Epoxy systems and amine polymer systems and methods for making the same

ABSTRACT

Compositions and methods for forming surfactants, aqueous dispersions, and curing agents are provided. In one aspect, the invention relates to improved epoxy functional surfactants prepared by reaction of an epoxy composition and an amidoamine composition formed from a blend of acid-terminated polyoxyalkylene polyols. The improved epoxy functional surfactants may be reacted with an excess of epoxy composition and water to result in an aqueous dispersion. The amidoamone composition may be a reaction mixture of a diamine compound and an acid terminated polyoxyalkylene composition formed from two or more polyoxyalkylene polyol compounds. The epoxy functional surfactant may be reacted with amine compounds to form a compound suitable as a curing agent.

FIELD OF THE INVENTION

The invention relates to surfactants and aqueous dispersions of epoxyresins. In one aspect, the invention relates to improved aminefunctional surfactants and to improved epoxy functional surfactantsprepared by reaction of an epoxy composition and an amine compositionformed from a blend of polyoxyalkylene polyols.

BACKGROUND OF THE INVENTION

Aqueous dispersions of epoxy resins have been known for many years.However, the performance of these dispersions as elements of coatingshas been viewed as inferior to their solvent borne counterparts. It isknown that the surfactants employed to render the epoxy componentemulsifiable such as nonylphenol ethoxylates, alkylphenol initiatedpoly(oxyethylene) ethanols, alkylphenol initiated poly(oxypropylene)poly(oxyethylene) ethanols, and block copolymers containing an internalpoly(oxypropylene) block and two external poly(oxyethylene) ethanolblocks readily migrate to surface interfaces where, it is speculated,they deleteriously affect film performance.

Moreover, as aqueous dispersions of epoxy resins have become more widelyused in industry, improved handling properties such as storage stabilityare required. The storage stability of many water borne epoxydispersions degrades over time due to the presence of amine nitrogenatoms in the surfactant molecules. As the pH of water borne dispersionsincreases over 9.8, the storage stability can no longer be measured inyears, but rather is measured in months.

It would also be desirable to decrease the particle size of the solids,or decrease the amount of surfactant required at a given solids level,or to disperse solids at a given particle size using less surfactant.Often, a larger amount of surfactant needed to decrease the particlesize and effectively disperse the solids in water leads to increased pHand reduced storage stability. Decreasing the surfactant level tocontrol the pH causes an increase in particle size.

Therefore, there is a need to form improved surfactants for formingaqueous dispersions of epoxy resins.

SUMMARY OF THE INVENTION

Embodiments of the invention are directed to surfactants for use inaqueous dispersions of epoxy resins and for use in amine polymercompositions. The surfactants may be further modified functionally foruse as curing agents in epoxy compositions. In one aspect, the inventionrelates to improved epoxy functional surfactants prepared by reaction ofan epoxy composition and an amidoamine composition formed from a blendof acid-terminated polyoxyalkylene polyols.

In one aspect of the invention an amidoamine composition is provided,including a reactant product of an acid terminated polyoxyalkylenecomposition of two or more acid terminated polyoxyalkylene polyolcompounds, wherein the acid terminated polyoxyalkylene composition has apolydispersity of 1.1 or greater and the two or more acid terminatedpolyoxyalkylene polyol compounds have from about 50% to about 100% ofcarboxylic end groups oxidized from hydroxyl end groups and a diaminecompound comprising a first amine substituent group of a primary aminesubstituent group and a second amine substituent group of a primaryamine substituent group or a secondary amine substituent group, whereinthe reaction product comprises an amidoamine compound having the formulaof:

wherein each of R₁ and R₂ comprises a hydrogen atom or a substituentgroup selected from the group of a branched or linear aliphatic, acycloaliphatic, an aromatic substituent group and combinations andsubsets thereof, having 1 to 21 carbon atoms, with at least one of R₁and R₂ comprising a hydrogen atom, R₃ is a divalent hydrocarbonsubstituent group selected from the group of a branched or linearaliphatic, a cycloaliphatic, an aromatic substituent group, andcombinations and subsets thereof, having 2 to 18 carbon atoms, n is anaverage number from about 18 to about 500, X is a hydrogen atom or asubstituent group selected from the group consisting of a methylsubstituent, an ethyl substituent, a hydroxymethyl substituent group,and combinations thereof, and Y is a hydrogen atom or a substituentgroup selected from the group of a methyl substituent, an ethylsubstituent, a hydroxymethyl substituent group, and combinationsthereof.

In another aspect of the invention, a method for forming an amidoaminecomposition is provided including providing an acid terminatedpolyoxyalkylene composition of two or more acid terminatedpolyoxyalkylene polyol compounds, wherein the acid terminatedpolyoxyalkylene composition has a polydispersity of 1.1 or greater andthe two or more acid terminated polyoxyalkylene polyol compounds havefrom about 50% to about 100% of carboxylic end groups oxidized fromhydroxyl end groups, providing a diamine compound comprising a firstamine substituent group of a primary amine substituent group and asecond amine substituent group of a primary amine substituent group or asecondary amine substituent group, and reacting the acid terminatedpolyoxyalkylene composition and the first diamine compound to form areaction product, wherein the reaction product comprises an amidoaminecompound having the formula of:

wherein each of R₁ and R₂ comprises a hydrogen atom or a substituentgroup selected from the group of a branched or linear aliphatic, acycloaliphatic, an aromatic substituent group and combinations andsubsets thereof, having 1 to 21 carbon atoms, with at least one of R₁and R₂ comprising a hydrogen atom, R₃ is a divalent hydrocarbonsubstituent group selected from the group of a branched or linearaliphatic, a cycloaliphatic, an aromatic substituent group, andcombinations and subsets thereof, having 2 to 18 carbon atoms, n is anaverage number from about 18 to about 500, X is a hydrogen atom or asubstituent group selected from the group consisting of a methylsubstituent, an ethyl substituent, a hydroxymethyl substituent group,and combinations thereof, and Y is a hydrogen atom or a substituentgroup selected from the group of a methyl substituent, an ethylsubstituent, a hydroxymethyl substituent group, and combinationsthereof.

In another aspect of the invention, an epoxy composition is providedincluding a reaction product prepared by reacting an epoxy component andan amidoamine composition, wherein the reaction product comprises anepoxy-functional surfactant having the structure:

and m is from 1 to 11, n is from 1 to 3, q is from 0 to 8, p is fromabout 18 to about 500, X is a hydrogen atom, a methyl substituent, anethyl substituent, a hydroxymethyl substituent group, subsets thereof,or combinations thereof, and each Y is a hydrogen atom, a methylsubstituent, an ethyl substituent, a hydroxymethyl substituent group,subsets thereof, or combinations thereof, and R₁₇ may be an alkyl group,an aryl group, an acyl group, and subsets and combinations thereof.

BRIEF DESCRIPTION OF THE DRAWING

The advantages and further aspects of the disclosure will be readilyappreciated by those of ordinary skill in the art as the same becomesbetter understood by reference to the following detailed descriptionwhen considered in conjunction with the accompanying drawings in whichlike reference characters designate like or similar elements throughoutthe several figures of the drawing and wherein:

FIG. 1 is a graph illustrating epoxy dispersion particle size stabilityat 25° C. for epoxy dispersions as formed with the material and processdescribed herein as compared to the prior art epoxy dispersions.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the invention are directed to surfactants for use inaqueous dispersions of epoxy resins and for use in amine polymercompositions. The surfactants may be further modified functionally foruse as curing agents in epoxy compositions. In one aspect, the inventionrelates to improved epoxy functional surfactants prepared by reaction ofan epoxy composition and an amidoamine composition formed from a blendof acid-terminated polyoxyalkylene polyols.

Some embodiments of the invention are directed to forming surfactantsfrom blends of two or more acid terminated polyoxyalkylenepolyol-containing compounds (also known as oxidized polyoxyalkylenepolyols and carboxylated polyoxyalkylenes) having different molecularweights. One surfactant may be a polyamidoamine functionalizedpolyoxyalkylene prosurfactant made from the acid terminatedpolyoxyalkylene polyol-containing compounds blend. The polyamidoaminefunctionalized polyoxyalkylene surfactants may then be further reactedto form epoxy functional surfactants, which may be formed separate or insitu with an epoxy resin. The epoxy functional surfactants may be usedto form aqueous epoxy dispersions. The epoxy functional surfactants mayalso be further reacted to form amine terminated surfactants, whichamine-terminated surfactants may be used for aqueous amine polymerdispersions or as curing agents for epoxy compositions. Thermosetcoatings and fiber size formulations may be made from the dispersionsdescribed herein.

It was surprisingly and unexpectedly discovered that blends of partiallyoxidized polyoxyalkylene polyols of dissimilar molecular weight provideunexpected superior reactive surfactants for emulsifying epoxyfunctional and amine functional polymers into “resin in water”dispersions. The superior properties observed included reduced particlesize and improved shelf life with improved (higher) non-volatilescontent and improved (lower) viscosity epoxy polymer dispersions.

In one aspect of the invention, an amidoamine composition of theprosurfactant described herein is formed from a reactant product of anacid terminated polyoxyalkylene polyol-containing composition of two ormore acid terminated polyoxyalkylene polyol compounds having a combinedpolydispersity of 1.1 or greater, the polyoxyalkylene polyol compoundsbeing oxidized from about 50% to about 100% conversion of hydroxyl tocarboxyl group, and a diamine compound comprising a first aminesubstituent group of a primary amine substituent group and a secondamine substituent group of a primary amine substituent group or asecondary amine substituent group.

Manufacture of an Amidoamine Compound and Composition

In one aspect, an amidoamine compound, such as a polyamidoaminefunctionalized polyoxyalkylene prosurfactant (also referred to herein asamidoamine prosurfactant) that is formed by the processes describedherein may have the formula of:

R₁ is a hydrogen atom or a substituent group selected from the group ofa branched or linear aliphatic, a cycloaliphatic, an aromaticsubstituent, and combinations and subsets thereof, having 1 to 21 carbonatoms. R₂ is a hydrogen atom or a substituent group selected from thegroup of a branched or linear aliphatic, a cycloaliphatic, an aromaticsubstituent, and combinations and subsets thereof, having 1 to 21 carbonatoms, with at least one of R₁ and R₂ comprising a hydrogen atom. R₃ isa divalent hydrocarbon substituent group selected from the group of abranched or linear aliphatic, a cycloaliphatic, an aromatic substituentgroup, and combinations and subsets thereof, having 2 to 18 carbonatoms, m may be 1, 2, or 3, and n may be an average number from about 18to about 500. For the repeating units x may be a hydrogen atom or asubstituent group selected from the group of a methyl substituent, anethyl substituent, a hydroxymethyl substituent group, and combinationsthereof. Y may be a hydrogen atom or a substituent group selected fromthe group of a methyl substituent, an ethyl substituent, a hydroxymethylsubstituent group, and combinations thereof. The oxyalkylenes may berandom or block polymerized.

The polyamidoamine functionalized polyoxyalkylene prosurfactant ofFormula (I) may have an amine value from about 8 to about 30, such asfrom about 12 to about 24, for example, from about 14 to about 18. Thepolyamidoamine functionalized polyoxyalkylene prosurfactant may behydrophilic.

The polyamidoamine functionalized polyoxyalkylene prosurfactant ofFormula (I) may have a weight average molecular weight (M_(w)) fromabout 200 to about 22,000, such as from about 2,000 to about 12,000, forexample, about 4,000 to about 10,000. The number average molecularweight (M_(n)) may be from about 180 to about 20,000, such as from about1,800 to about 11,000, for example, about 3,000 to about 8,000. Thenumber average (nominal) molecular weight represents the total weight ofthe polymer divided by the total number of molecules in the totalweight.

Additionally, the molecular weight distribution may be further addressedwith regard to a Z-average molecular weight (M_(Z)) and a Z+1 averagemolecular weight (M_(Z+1)) as commonly understood to one skilled in theart with regard to molecular weight distribution analysis. The Z-averagemolecular weight (M_(Z)) may be from about 300 to about 30,000, such asfrom about 3,000 to about 20,000, for example, about 5,000 to about14,000. The Z+1 average molecular weight (M_(Z+1)) may be from about 400to about 40,000, such as from about 4,000 to about 27,000, for example,from about 6,500 to about 19,000.

In one aspect, the polyamidoamine functionalized polyoxyalkyleneprosurfactant may be formed from two or more acid terminatedpolyoxyalkylene polyol-containing compounds (also known as oxidizedpolyoxyalkylene polyol and carboxylated polyoxyalkylenes) havingdifferent molecular weights that are reacted with at least one diamineas described herein.

The at least one diamine compound may include a first amine substituentgroup of a primary amine substituent group and a second aminesubstituent group of a primary amine substituent group or a secondaryamine substituent group. The reaction may occur with or without anexcess of diamine, including an amine to acid equivalent ratio fromabout 12:1 to about 2:3.

Alternatively, the polyamidoamine functionalized polyoxyalkyleneprosurfactant may be formed from an acid terminated polyoxyalkylenepolyol-containing compound reacted with at least one diamine. Thecompound of at least one diamine may include a first amine substituentgroup of a primary amine substituent group and a second aminesubstituent group of a secondary amine substituent group. The reactionmay occur with an excess of diamine, including an amine to acidequivalent ratio from about 3:1 to about 1:2.

In one embodiment of the prosurfactant, the polyamidoaminefunctionalized polyoxyalkylene prosurfactant may be formed from a blendof two or more acid terminated polyoxyalkylene polyol-containingcompounds having different molecular weights as described herein thatare reacted with the at least one diamine. For example, a blend of afirst acid terminated polyoxyalkylene polyol-containing compound and asecond acid terminated polyoxyalkylene polyol-containing compound havinga molecular weight higher than the molecular weight of the first acidterminated polyoxyalkylene polyol-containing compound, which compoundsare reacted with the at least one diamine. The reaction may occur withan amine to acid equivalent ratio from about 12:1 to about 1:2.

In another aspect, the polyamidoamine functionalized polyoxyalkyleneprosurfactant may be formed by separately forming amidoamines from twoor more acid terminated polyoxyalkylene polyol-containing compounds andthen combining the products of the reactions into a blend ofpolyamidoamine functionalized polyoxyalkylene prosurfactant. Eachreaction may be with at least one diamine as described herein and eachreaction may have the same or different diamine. Each of the reactionsmay be performed with the processes described herein and may occur withan amine to acid equivalent ratio of from about 12:1 to about 1:2.

One embodiment of the prosurfactant composition involves forming anamidoamine mixture from a blend of two acid terminated polyoxyalkylenepolyol-containing compounds together in a blend ratio from about 3:17 toabout 17:3, such as a blend ratio of about 11:9, of a first molecularweight acid terminated polyoxyalkylene polyol with a second molecularweight acid terminated polyoxyalkylene polyol. Alternatively, the blendmay be from about 15 wt. % to about 85 wt. %, for example, about 45%, ofa first molecular weight acid terminated polyoxyalkylene polyol and fromabout 85 wt. % to about 15 wt. %, for example, about 55%, of a secondmolecular weight acid terminated polyoxyalkylene polyol. The second acidterminated polyoxyalkylene polyol-containing compound has a molecularweight higher than the molecular weight of the first acid terminatedpolyoxyalkylene polyol-containing compound. The first molecular weightacid terminated polyoxyalkylene polyol may have a weight averagemolecular weight from about 200 to about 5,000, such as from about 2,000to about 5,000 as described below, and the second molecular weight acidterminated polyoxyalkylene polyol may have a weight average molecularweight from greater than 4,000 to about 16,000 as described below.

The acid terminated polyoxyalkylene polyol-containing compounds may havethe formula:

R₃ may be a hydrogen atom or a divalent hydrocarbon substituent groupselected from the group of a branched or linear aliphatic, acycloaliphatic, an aromatic substituent group, and combinations andsubsets thereof, having 2 to 18 carbon atoms, and the hydrocarbonsubstituent group has a hydroxyl-terminus group or a carboxyl-terminusgroup. For the repeating units, in may be from 1-11 and n may be anaverage number from about 18 to about 500 for each of the respectiveacid terminated polyoxyalkylene polyol-containing compounds. X may be ahydrogen atom, a methyl substituent, an ethyl substituent, or ahydroxymethyl substituent group. Y may be a hydrogen atom, a methylsubstituent, an ethyl substituent, or a hydroxymethyl substituent group.The acid-terminated polyoxyalkylene polyol-containing compounds may berandom or block polymers. The polyoxyalkylene polyol-containingcompounds may have from about 50% to 100%, such as from about 70% toabout 95%, of the hydroxyl end groups oxidized to form the acidterminated substituent groups (carboxylic acid end groups/carboxyl endgroups).

The weight average molecular weight (M_(w)) of the acid terminatedpolyoxyalkylene polyol-containing compound of Formula (IIa) may be fromabout 200 to about 22,000, such as from about 2,000 to about 10,000, forexample, about 4,000 to about 10,000. The number average molecularweight (M_(n)) may be from about 180 to about 20,000, such as from about1, 800 to about 11,000, for example, about 3,000 to about 8,000. Thenumber average (nominal) molecular weight represents the total weight ofthe polymer divided by the total numbers of moles of molecules which thepolymer contains.

Additionally, the molecular weight distribution may be further addressedwith regard to a Z-average molecular weight (M_(Z)) and a Z+1 averagemolecular weight (M_(Z+1)) as commonly understood to one skilled in theart with regard to molecular weight distribution analysis. The Z-averagemolecular weight (M_(Z)) may be from about 300 to about 30,000, such asfrom about 3,000 to about 20,000, for example, about 5,000 to about14,000. The Z+1 average molecular weight (M_(Z+1)) may be from about 400to about 40,000, such as from about 4,000 to about 27,000, for example,from about 6,500 to about 19,000.

For a combined composition of two or more acid terminatedpolyoxyalkylene polyol-containing compound, the composition may have apolydispersity of greater than about 1.1. In one aspect, such acomposition may have a polydispersity from about 1.15 to about 5, suchas from about 1.22 to about 1.70. The polydispersity is calculated bythe division of the weight average molecular weight (M_(W)) by thenumber average molecular weight (M_(N)).

Examples of suitable acid terminated polyoxyalkylene polyol-containingcompounds include acid terminated polyoxyethylene glycols, acidterminated polypropylene glycols, and combinations thereof. For example,each of the two or more acid terminated polyoxyethyleneglycol-containing compounds may have the formula:

N may be an average number from about 18 to about 500 for each of therespective polyoxyalkylene glycol compounds. For the repeating units, inmay be from 1-11 and n may be an average number from about 18 to about500 for each of the respective acid terminated polyoxyethyleneglycol-containing compounds. X may be a hydrogen atom, a methylsubstituent, an ethyl substituent, or a hydroxymethyl substituent group.Y may be a hydrogen atom, a methyl substituent, an ethyl substituent, ora hydroxymethyl substituent group. The acid terminated polyoxyethyleneglycol-containing compounds may be random or block polymers. Thepolyoxyethylene glycol-containing compounds may have from about 50% to100%, such as from about 70% to about 95%, of the hydroxyl end groupsoxidized to form the carboxylic acid end groups.

The weight average molecular weight of the acid terminatedpolyoxyethylene glycol-containing compound of Formula (IIb) may be fromabout 200 to about 22,000, such as from about 2,000 to about 10,000, forexample, about 4,000 to about 10,000. The number average molecularweight (M_(n)) may be from about 180 to about 20,000, such as from about1, 800 to about 11,000, for example, about 3,000 to about 8,000. Thenumber average (nominal) molecular weight represents the total weight ofthe polymer divided by the total numbers of moles of molecules which thepolymer contains.

Additionally, the molecular weight distribution may be further addressedwith regard to a Z-average molecular weight (M_(Z)) and a Z+1 averagemolecular weight (M_(Z+1)) as commonly understood to one skilled in theart with regard to molecular weight distribution analysis. The Z-averagemolecular weight (M_(Z)) may be from about 300 to about 30,000, such asfrom about 3,000 to about 20,000, for example, about 5,000 to about14,000. The Z+1 average molecular weight (M_(Z+1)) may be from about 400to about 40,000, such as from about 4,000 to about 27,000, for example,from about 6,500 to about 19,000.

In one embodiment, a composition of the acid terminated polyoxyalkyleneglycol-containing compounds may be formed by oxidizing a mixture of twoor more polyoxyalkylene polyol compounds, such as two or morepolyoxyalkylene glycol compounds. Alternatively, a composition of theacid terminated polyoxyalkylene glycol-containing compounds may beformed by independently oxidizing each of two or more polyoxyalkylenepolyol compounds, such as two or more polyoxyalkylene glycol compounds,and then combining the respective acid terminated polyoxyalkylenepolyol-containing compounds into one composition.

Either oxidized separately and then combined or oxidized in combination,the blend ratio of two polyoxyalkylene polyol compounds may be fromabout 3:17 to about 17:3, such as a blend ratio from about 4:1 to about1:4, for example about 11:9, of a first molecular weight polyoxyalkylenepolyol to a second molecular weight polyoxyalkylene polyol.Alternatively, the blend ratio may be represented by a weight percentfrom about 15 wt. % to about 85 wt. %, for example, about 45%, of afirst molecular weight polyoxyalkylene polyol and from about 85 wt. % toabout 15 wt. %, for example, about 55%, of a second molecular weightpolyoxyalkylene polyol. The second polyoxyalkylene polyol has amolecular weight higher than the molecular weight of the firstpolyoxyalkylene polyol.

Polyoxyalkylene polyol compounds may be oxidized orcarboxylated/acidified to form acid terminated polyoxyalkylenepolyol-containing compounds by oxidation of the polyoxyalkylene polyolsincluding, but not limited to, the processes described in U.S. Pat. No.6,235,931, which is incorporated herein by reference to the extent notinconsistent with the claimed aspects and description herein.

In an embodiment of one formation process, oxygen-containing gas isadded to the polyoxyalkylene polyol in the presence of a free radical(e.g., 2,2,6,6-tetramethyl-1-piperidinyloxy) and an inorganic acid(e.g., nitric acid) in water to oxidize the hydroxyl groups tocarboxylic acid groups. If diacid-terminated polyalkylene polyol isdesired, substantially all of the alcohol groups are oxidized tocarboxylic acid groups. The acid-terminated polyalkylenepolyol-containing compounds may also be made by Williamson ethersynthesis where a polyoxyalkylene polyol is reacted with chloroaceticacid and/or esters in the presence of a base.

In one embodiment of the reaction conditions, the temperature may befrom about 20° C. to about 70° C., and at pressures in the range of fromabout atmospheric pressure up to about 100 psig. Following the reaction,the remaining inorganic acid and water is distilled from the reactor.

In one embodiment, the composition of two acid terminatedpolyoxyalkylene polyol-containing compounds may be formed by oxidizing amixture of first molecular weight and second molecular weightpolyoxyalkylene polyol compounds, such as polyoxyethylene glycols,having different molecular weights at a blend ratio from about 3:17 toabout 17:3, such as a blend ratio of about 11:9, of a first molecularweight polyoxyalkylene polyol to a second molecular weightpolyoxyalkylene polyol. The first molecular weight polyoxyalkylenepolyol may have a molecular weight from 200 to about 5,000, and thesecond molecular weight polyoxyalkylene polyol may have a molecularweight from greater than 4,000 to about 16,000. The second molecularweight polyoxyalkylene polyol has a higher molecular weight than thefirst molecular weight polyoxyalkylene polyol.

The polyoxyalkylene polyols described herein include, and are notlimited to, polyoxyalkylene polyols polymerized by alkali metal anddouble metal cyanide catalyst. The polyoxyalkylene polyols may beself-initiated with water, initiated with any glycol, including, and notlimited to, liquid diols or glycerine, initiated with bisphenols, orinitiated with other active hydrogen organic compounds including primaryor secondary amines.

Examples of suitable polyalkylene polyol compounds may have the formula:

R₃ may be a hydrogen atom or a divalent hydrocarbon substituent groupselected from the group of a branched or linear aliphatic, acycloaliphatic, an aromatic substituent group, and combinations andsubsets thereof, having 2 to 18 carbon atoms, and each of thehydrocarbon substituent groups may have a hydroxyl-terminus group. Forthe repeating units, m may be from 1-11 and n may be an average numberfrom about 18 to about 500 for each of the polyoxyalkylene polyolcompounds. X may be a hydrogen atom, a methyl substituent, an ethylsubstituent, a hydroxymethyl substituent group, a hydroxyl-terminusgroup, and subsets and combinations thereof. Y may be a hydrogen atom, amethyl substituent, an ethyl substituent, a hydroxymethyl substituentgroup, a hydroxyl-terminus group, and subsets and combinations thereof.Suitable polyoxyalkylene polyols include polyoxyethylene (polyether)glycols (PEG), polypropylene polyether glycols, 1,2 polybutylenepolyether glycols, 1,4 polybutylene polyether glycols, and combinationsthereof. Each of the polyoxyalkylene glycols may comprise apolyoxyethylene glycol monoalkylether or a monoalkylether of a blockcopolymer of ethylene oxide and propylene oxide or butylene oxide(“polyoxyalkylene glycol”), or a block copolymer of ethylene oxide andpropylene oxide or polybutylene oxide (“polyoxyalkylene glycol”).

Examples of suitable polyoxyethylene glycol (PEG) compounds may have theformula:

For the repeating units, m may be from 1-11 and n may be an averagenumber from about 18 to about 500 for example, about 230 for highermolecular weight compounds, and n may be from 5 to 150, for example,about 91, for lower molecular weight compounds. X may be a hydrogenatom, a methyl substituent, an ethyl substituent, a hydroxymethylsubstituent group, a hydroxyl-terminus group, and subsets andcombinations thereof. Y may be a hydrogen atom, a methyl substituent, anethyl substituent, a hydroxymethyl substituent group, ahydroxyl-terminus group, and subsets and combinations thereof.

For the repeating units, m may be from 1 to 11 and n may be from 18 to500, for example, about 230, for higher molecular weight compounds, andn may be from 5 to 150, for example, about 91, for lower molecularweight compounds.

Either individually or in combination, the number average molecularweight (M_(n)) of polyoxyalkylene glycol compounds may be from about 180to about 20,000, such as from about 1,800 to about 11,000, for example,about 3,000 to about 8,000. The number average (nominal) molecularweight represents the total weight of the polymer divided by the totalnumbers of molecules the polymer contains. Either individually or incombination, the weight average molecular weight (M_(w)) ofpolyoxyalkylene glycol compounds may be from about 200 to about 22,000,such as from about 2,000 to about 10,000, for example, about 4,000 toabout 10,000.

Additionally, the molecular weight distribution may be further addressedwith regard to a Z-average molecular weight (M_(Z)) and a Z+1 averagemolecular weight (M_(Z+1)) as commonly understood to one skilled in theart with regard to molecular weight distribution analysis. The Z-averagemolecular weight (M_(Z)) may be from about 300 to about 30,000, such asfrom about 3,000 to about 20,000, for example, about 5,000 to about14,000. The Z+1 average molecular weight (M_(Z+1)) may be from about 400to about 40,000, such as from about 4,000 to about 27,000, for example,from about 6,500 to about 19,000.

For a combined composition of two or more polyoxyalkylene polyols, thecomposition may have a polydispersity of greater than about 1.1, such asfrom 1.15 to 1.70 or from 1.25 to about 1.55, for example, about 1.35 toabout 1.45, which is calculated by the division of the weight averagemolecular weight (M_(W)) by the number average molecular weight (M_(n)).

In on example, the first molecular weight polyoxyalkylene polyolcompound may have n in the range of 5 to 150, such as from 45 to 115,for example, about 91, providing for a first number average molecularweight from about 2,000 to about 5,000, such as about 4000 and a firstweight average molecular weight from about 2,200 to about 5,500, such asabout 4,400. The second molecular weight polyoxyalkylene polyol compoundmay have n in the range of about 18 to about 500, such as from about 90to about 365, for example, about 230, providing for a second numberaverage molecular weight from about 4,000 to about 18,000, such as fromabout 4,000 to about 16,000, for example, about 8000 and a second weightaverage molecular weight from about 4,400 to about 17,600, such as about8,800. In one example, the respective first weight average molecularweight and second weight average molecular weight polyoxyalkylene polyolcompounds may be mixed in a molar ratio of about 45:55. The averagevalue on n in the blend may be from about 100 to about 205, for example,n may be about 150.

Polyoxyalkylene polyols generally contain a distribution of compoundswith a varying number of oxyethylene units and/or other oxyalkyleneaverage units, and the quoted number of units is the whole real numberclosest to the statistical average and the peak of the distribution.Whole real number as used herein refers to a number which is a positiveinteger or fractions of integers.

The acid terminated polyoxyalkylene polyol-containing compounds, eitherindividually or in combination, may then be reacted with at least onepolyamine compound, such as at least one diamine compound, to form thepolyamidoamine functionalized polyoxyethylene prosurfactant as describedherein.

The reaction is performed in a reaction vessel under condensationconditions. Suitable reaction conditions involve heating the startingmaterials at temperatures ranging from about 100° C. to about 250° C.,at atmospheric pressure, and distilling the condensation by-product,water. Along with water, excess polyamine compounds may also be removedby distillation. To further improve the removal of water and any excesspolyamine compounds, a vacuum or reduced vessel pressure, such as fromabout 10 to about 200 mmHg (Torr) may be used following the initialreaction.

In one embodiment of the diamine compound, each amine group of thediamine compound is a primary amine, and the diamine compound has theformula:H₂N—R₃—NH₂  (IV).

R₃ is a divalent hydrocarbon substituent group selected from the groupof a branched or linear aliphatic, a cycloaliphatic, an aromaticsubstituent group, and combinations and subsets thereof, having 2 to 18carbon atoms. The divalent hydrocarbon substituent group may optionallycontain one or more non-reactive oxygen and/or nitrogen atoms, in thebackbone. The nitrogen atoms may be present up to an average of 4secondary and/or tertiary nitrogen atoms per structure in the R₃ group.Oxygen atoms may be present up to an average of 4 atoms or less in theR₃ group. Thus, Formula (IV) includes di-secondary amine compoundsincluding the formula HR₂N—R₃—NHR₂, and R₂ is a substituent groupselected from the group of a branched or linear aliphatic, acycloaliphatic, an aromatic substituent, and combinations and subsetsthereof, having 1 to 21 carbon atoms.

Examples of suitable diamines include, for example, m-xylylenediamine,1,3-bis(aminomethyl)cyclohexane, 2-methyl-1,5-pentanediamine,1,3-pentanediamine, ethylenediamine, diethylenetriamine,triethylenetetramine, polyoxypropylenediamines,2,2(4),4-trimethyl-1,6-hexanediamine, isophorone diamine,2,4(6)-toluenediamine, 1,6-hexanediamine, 1,2-diaminocyclohexane,para-diaminodicyclohexyl methane (PACM), and combinations thereof.Suitable oxygen-containing amines include, for example,1,10-diamino-4,7-dioxadecane, 1,8-diamino-3,6-dioxaoctane,1,13-diamino-4,7,10-trioxamidecane, and combinations thereof.

The amine according to formula (IV) may be added in a molar excess overthe acid terminated polyoxyalkylene polyol-containing compounds. Theexcess diamine compounds may be added at a molar ratio to the carboxylicacid functional groups from about 6:1 to about 2:1, such as from about5:1 to about 3:1, for example, from about 4:1 to about 3.2:1. When anexcess amount of diamine compounds is used, non-reacted diaminecompounds may be removed following the reaction.

Additionally, a monoepoxy compound may be introduced concurrently orsequentially with the diamine to further form the polyamidoaminefunctionalized polyoxyalkylene prosurfactant. The monoepoxy compound maybe a monoepoxy compound as described herein, and may include, forexample, a glycidyl ester of a C₁₀ tertiary carboxylic acid. Themonoepoxy compound may be added at an amount sufficient to control theamount of diepoxy hydrophobe to about 5% to about 40% hydrophobe in asubsequent diepoxy component addition, such as to form an epoxy terminalsurfactant and/or an epoxy dispersion.

The reaction temperature between the amidoamine composition and theoptional addition of the monoepoxy compounds is not limited. Suitablereaction temperatures range from about 60° C. to about 150° C. and at avacuum or reduced vessel pressure, such as from about 1 KPa to about 30KPa.

Suitable monoepoxy compounds include:

-   -   wherein R₄ and R₆ are the same or different and are a branched        or linear alkyl, cycloalkyl, polyoxyalkyl, or alkenyl        substituent having from 2 to 100 carbon atoms, optionally        branched; and R₅ is hydrogen or a branched or unbranched alkyl        having 1-18 carbon atoms. There may be more than one type of R₅        group attached to the aromatic ring. R₁₅ is a divalent alkyl or        aryl substituent having from 3 to 20 carbon atoms.

The categories would include the oxiranes of olefins including butyleneoxide, cyclohexene oxide, styrene oxide; glycidyl ethers of monovalentalcohols such as methyl, ethyl, butyl, 2-ethylhexyl, and dodecylalcohols; glycidyl ethers of the alkylene oxide adducts of alcoholshaving at least 8 carbon atoms by the sequential addition of alkyleneoxide to the corresponding alkanol (ROH), such as those marketed underthe Neodol® name; glycidyl ethers of monovalent phenols such as phenol,cresol, and other phenols substituted in the o- or p-positions withC₁-C₂₁ branched or unbranched alkyl, aralkyl, alkaryl, or alkoxy groupssuch as nonylphenol; glycidyl esters of mono-carboxylic acids such asthe glycidyl ester of caprylic acid, the glycidyl ester of capric acid,the glycidyl ester of lauric acid, the glycidyl ester of stearic acid,the glycidyl ester of arachidic acid and the glycidyl esters of alpha,alpha-dialkyl monocarboxylic acids described in U.S. Pat. No. 3,178,500,hereby incorporated by reference; glycidyl esters of unsaturatedalcohols or unsaturated carboxylic acids such as the glycidyl ester ofneodecanoic acid; epoxidized methyl oleate, epoxidized n-butyl oleate,epoxidized methyl palmitoleate, epoxidized ethyl linoleate and the like;allyl glycidyl ether, and acetals of glycidaldehyde.

Specific examples of monoglycidyl capping agents include alkyl glycidylethers with 1-18 linear carbon atoms in the alkyl chain such as butylglycidyl ether or a mixture of C₈-C₁₄ alkyls, cresyl glycidyl ether,phenyl glycidyl ether, nonylphenylglycidyl ether, p-tert-butylphenylglycidyl ether, 2-ethylhexyl glycidyl ether, the glycidyl ester ofneodecanoic acid, and combinations thereof. Additional examples ofsuitable monoepoxies include the glycidated monoacids and epoxidesformed from alpha olefins and glycidoxyalkylalkoxysilanes.

Commercial examples of preferred monoepoxy resins include, for example,HELOXY® Modifiers 62, 63, 64, 65, and 116, and CARDURA® Resin E-10 allavailable from Momentive Specialty Chemicals of Columbus Ohio.

The aliphatic based monoepoxy compounds are usually hydrophobic incharacter, which tends to improve the coalescence properties of theepoxy-curing agent mixture in which the monoepoxy compounds are used atlow temperatures, and tends to lower the glass transition temperature ofthe film or coating. The lower glass transition temperature improves theimpact strength of the cured film. Aromatic based monoglycidyl monoepoxycompounds may have the advantage of rendering the cured film more rigid,chemically resistant, and resistant to stresses at high temperatures.Any one of these types of the monoepoxy compounds may be used, andcombinations thereof are also advantageous to attain an overall balanceof solubility, coalescence, mechanical strength and chemical resistancein the final products.

Alternatively, in another embodiment of the diamine, one amine group isa primary amine, and the other amine group is a secondary amine, and thediamine may have the formula:R₁—HN—R₃—NH₂  (V).

R₃ is a divalent hydrocarbon substituent group selected from the groupof a branched or linear aliphatic, a cycloaliphatic, an aromaticsubstituent group, and combinations and subsets thereof, having 2 to 18carbon atoms, and optionally containing one or more non-reactive oxygenatoms and/or nitrogen atoms in the backbone. R₁ is a branched or linearaliphatic, a cycloaliphatic, or an aromatic divalent group having 1 to21 carbon atoms, and optionally containing one or more non-reactiveoxygen or nitrogen atoms in the backbone. Each of R₁ and R₃ may furtherhave a terminal substituent group selected from the group of an alkylgroup (i.e., a methyl group), a hydroxyl group, an alkylthio group, andcombinations and subsets thereof. Alternatively, R₁ and R₃ may compriseone common ring.

Alternatively, Formula (V) may be modified to have a second R₁ group onthe second nitrogen atom. Thus, Formula (V) may include di-secondaryamine compounds including the formula HR₁N—R₃—NHR₁, and R₁ is asubstituent group selected from the group of a branched or linearaliphatic, a cycloaliphatic, an aromatic substituent, and combinationsand subsets thereof, having 1 to 21 carbon atoms.

Examples of suitable diamines containing one primary and one secondaryamine group include, for example, N-methylethylenediamine,N-butyl-1,6-hexanediamine, N-cyclohexyl-1,3-propanediamine,N-(2-aminoethyl)piperazine, aminoethylethanolamine,N-methyl-1,4-cyclohexanediamine, N-oleyl-1,3-propanediamine,N-cocoalkyl-1,3-propanediamine, N-(methylthio)ethyl-1,3-propanediamine,N-(linear or branched decyl)oxypropyl-1,3-propanediamine, N-(linear orbranched tridecyl)oxypropyl-1,3-propanediamine,N-cocoalkyloxypropyl-1,3-propanediamine,N-(octyl/decyl)oxypropyl-1,3-propanediamine, and combinations thereof.

The amine according to formula (V) may be added in a ratio ofequivalents of carboxylic acid functional groups to moles of amine fromabout 2:1 to about 1:2, such as from about 3:2 to about 2:3, forexample, from about 3:2 to about 1:1. As such, in some embodiments, theamine according to formula (V) may be added without a molar excess overthe blend of two or more acid terminated polyoxyalkylenepolyol-containing compounds. Preferably, no monoepoxy is added, eitherconcurrently or subsequently, to the reaction with the amine compound offormula (V). Any excess amine material may be removed after the aminereaction and/or monoepoxy reaction.

Alternatively, the amine according to formula (V) may be added in aratio of equivalents of carboxylic acid functional groups to moles ofamine from about 2:1 to about 1:2, such as from about 3:2 to about 2:3,from about 3:2 to about 1:1 to a composition having one or more acidterminated polyoxyalkylene polyol-containing compounds. In such analternative embodiment, monoepoxy may be added concurrently orsubsequently to the reaction with the amine compound of formula (V). Anyexcess amine material may be removed after the amine reaction and/ormonoepoxy reaction.

In one aspect, the invention relates to improved epoxy functionalsurfactants for aqueous dispersions of epoxy resins. Once the amidoaminecomposition is manufactured, the epoxy functional surfactant is made byreacting the optionally partially end capped amidoamine composition withat least a diepoxy resin having a functionality greater than one epoxidegroup per molecule. The epoxy functional surfactant may be a non-ionicsurfactant formed in situ when reacted with an excess epoxy functionalcomposition. The epoxy component may be an epoxy resin or a mixture ofan epoxy resin and a phenolic compound. The polyamidoaminefunctionalized polyoxyethylene prosurfactant of the amidoaminecomposition is contacted with the epoxy component under conditionseffective to react the amine group and the epoxide group.

An epoxy functional surfactant may be prepared by reacting thepolyamidoamine functionalized polyoxyethylene prosurfactant formed fromthe original blend of polyoxyalkylene polyol compounds with at least oneepoxy component having a functionality greater then one epoxide pergroup under conditions effective to react the amine group and the epoxygroup. The epoxy component may have the same stoichiometric ratio orequivalent ratio, or may have a stoichiometric excess or equivalentexcess of epoxy substituent groups to amine groups. The equivalent ratioof the amine to epoxy may be at least 1:2, such as in the range of fromabout 1:6, to about 1:500, for example, in the range of from about 1:6to about 1:30.

The reaction is typically carried out at a temperature from ambienttemperature to an elevated temperature sufficient for reacting the aminegroup and the epoxide group, such as in the range of from about 50° C.to about 200° C. at atmospheric pressure for a time effective to producethe reaction products. The progress of the reaction can be monitored andtargeted to produce the desired product by measuring the epoxyequivalent weight of the reactant mixture. Generally, the reactionmixture is heated until the epoxy equivalents equal to the amineequivalents added are consumed which is generally one hour or greater.More than one epoxy resin can be reacted with the polyamidoaminefunctionalized polyoxyethylene prosurfactant.

The epoxy components used in producing the surfactant can be anyreactive epoxy resin having a 1,2-epoxy, oxirane, equivalency, on theaverage, greater than one epoxide group per molecule, and in someapplications, such from about 1.5 to about 6.5 epoxide groups permolecule. The epoxy resin can be saturated or unsaturated, linear orbranched, aliphatic, cycloaliphatic, aromatic or heterocyclic, and maybear substituents which do not materially interfere with the reactionwith the carboxylic acid. Such substituents can include bromine orfluorine. The epoxy resin may be monomeric or polymeric, liquid orsolid, but is preferably liquid or a low melting solid at roomtemperature. Generally epoxy components contain a distribution ofcompounds with a varying number of repeat units.

Suitable epoxy resins include glycidyl ethers prepared by reactingepichlorohydrin with a compound containing at least 1.5 aromatichydroxyl groups carried out under alkaline reaction conditions. Examplesof epoxy resins suitable for use in the invention include in addition tothe epoxy resins mentioned above, monoepoxies, diglycidyl ethers ofdihydric compounds, epoxy novolacs, cycloaliphatic epoxies, polyglycidylesters of polycarboxylic acids, glycidyl methacrylate-containing acrylicresins, and combinations thereof.

Further, the epoxy component can be a mixture of epoxy resins that maybe reacted with the polyamidoamine functionalized polyoxyethyleneprosurfactant. In one such embodiment, the epoxy resin can comprise amonoepoxide resin and a di- and/or a multi-functional epoxy resin,preferably an epoxy resin having a functionality of from about 0.7 toabout 1.3 and an epoxy resin having a functionality of at least 1.5,preferably—at least 1.7, more preferably from about 1.8 to about 2.5.The mixture can be added or reacted with the amidoamine compositionstepwise or simultaneously. For example, the polyamidoaminefunctionalized polyoxyethylene prosurfactant of the amidoaminecomposition can be reacted first with a monoepoxide resin and then witha diepoxy resin. In another example, the epoxy component can be reactedwith a novolac epoxy resin and a diepoxy resin stepwise or at the sametime in any order.

If desired the surfactant can be recovered from the reaction mixture ormade “in-situ.” To provide the surfactant in-situ in the desired epoxycomponent, the polyamidoamine functionalized polyoxyethyleneprosurfactant can be reacted into the desired epoxy component. For thein-situ method, the epoxy component should be present in an amountsufficient to provide unreacted epoxy component and the surfactantadduct.

The in-situ method may include providing an epoxy-functional amidoamineprosurfactant where the residue of the epoxy component (hydrophobicmoiety), which was reacted with the polyamidoamine functionalizedpolyoxyethylene prosurfactant, is the same as the bulk epoxy resin thatis dispersed. The residue of the epoxy component (hydrophobic moiety) isthe same as the bulk epoxy resin when the hydrophobic moiety from thesurfactant has the same IR spectrum as the IR spectrum of the bulk epoxyresin. When the surfactant is recovered, the equivalent ratio of theamine to epoxy is preferably within the range of from about 1:30 toabout 1:6.

Further, to provide the surfactant in-situ in an advanced epoxy resin,the amidoamine composition can be reacted into the mixtures of diepoxyresins, such as diglycidyl ethers of dihydric phenols, with dihydricphenols during the advancement reaction or can be reacted into the resinafter the advancement reaction. In an advancement reaction, generallythe diepoxy resin and the dihydric phenol are allowed to react in amolar ratio of about 7.5:1 to about 1.1:1 in the presence of anadvancement catalyst, producing an advanced epoxy resin having a weightper epoxy value of from about 225 to about 3,500. Typically, from about0.1 to about 15 weight percent of the amidoamine composition, based onepoxy resin or epoxy resin and phenolic compound, is used. It ispreferred to add the amidoamine composition after the advancementreaction, whether the advanced products are separated or provided as is.

Suitable diepoxy resins may include difunctional epoxy resins, di-epoxyresins, such as a diglycidyl ether of a dihydric phenol, a diglycidylether of a hydrogenated dihydric phenol, a branched or linear aliphaticglycidyl ether, epoxy novolac or a cycloaliphatic epoxy.

Diglycidyl ethers of dihydric phenols can be produced, for example, byreacting an epihalohydrin with a dihydric phenol in the presence of analkali. Examples of suitable dihydric phenols include:2,2-bis(4-hydroxyphenyl)propane (bisphenol-A);2,2-bis(4-hydroxy-3-tert-butylphenyl)propane;1,1-bis(4-hydroxyphenyl)ethane; 1,1-bis(4-hydroxyphenyl)isobutane;bis(2-hydroxy-1-naphthyl)methane; 1,5-dihydroxynaphthalene;1,1-bis(4-hydroxy-3-alkylphenyl)ethane and the like. Suitable dihydricphenols can also be obtained from the reaction of phenol with aldehydessuch as formaldehyde (bisphenol-F). Diglycidyl ethers of dihydricphenols include advancement products of the above diglycidyl ethers ofdihydric phenols with dihydric phenols such as bisphenol-A, such asthose described in U.S. Pat. Nos. 3,477,990 and 4,734,468, which areherein incorporated by reference.

Diglycidyl ethers of hydrogenated dihydric phenols can be produced, forexample, by hydrogenation of dihydric phenols followed by a glycidationreaction with an epihalohydrin in the presence of a Lewis acid catalystand subsequent formation of the glycidyl ether by reaction with sodiumhydroxide. Examples of suitable dihydric phenols are listed above.

Aliphatic glycidyl ethers can be produced, for example, by reacting anepihalohydrin with a branched or linear aliphatic diol or aryl diol inthe presence of a Lewis acid catalyst, and then by conversion of thehalohydrin intermediate to the glycidyl ether by reaction with sodiumhydroxide. Examples of preferred aliphatic glycidyl ethers include thosecorresponding to the formulas:

where:

-   -   p is an integer from 1 to 12, preferably from 1 to 4,    -   q is an integer from 4 to 24, preferably from 4 to 12, and    -   R₁₁ may be a divalent cycloaliphatic group having the structures        and formulas:

where R₁₂ and R₁₃ are each independently an alkylene group, or adivalent arylaliphatic group having the formula

where R₁₄ is an alkylene group. The term aliphatic or cycloaliphaticincludes compounds having oxygen and/or sulphur atoms in or on thebackbone.

Examples of suitable aliphatic glycidyl ethers include for example,diglycidyl ethers of 1,4 butanediol, neopentyl glycol,cyclohexanedimethanol, hexanediol, polypropylene glycol, and like diolsand glycols; and triglycidyl ethers of trimethylol ethane andtrimethylol propane.

Epoxy novolacs can be produced by condensation of formaldehyde and aphenol followed by glycidation by reaction with an epihalohydrin in thepresence of an alkali. The phenol can be for example, phenol, cresol,nonylphenol and t-butylphenol. Examples of the preferred epoxy novolacsinclude those corresponding to the formula:

wherein R₇ is independently a hydrogen or a C₁-C₁₀ alkyl group and r isa real number from 0 to 6. Epoxy novolacs generally contain adistribution of compounds with a varying number of glycidatedphenoxymethylene units, r. Generally, the quoted number of units is thenumber closest to the statistical average, and the peak of thedistribution.

Cycloaliphatic epoxies can be produced by epoxidizing acycloalkene-containing compound with more than one olefinic bond withperoxycarboxylic acids, such as peracetic acid. Examples of thepreferred cycloaliphatic epoxies include those corresponding to theformulas:

wherein R₁₀ is a divalent aliphatic group optionally containing ether orester group(s) or together with R₉ or R₈ forming a spiro ring optionallycontaining heteroatoms, and R⁹ and R⁸ are independently hydrogen or R₉or R₈ together with R₁₀ form a spiro ring optionally containingheteroatoms such as oxygen. Preferably R₁₀ contains from 1 to 20 carbonatoms. Examples of cycloaliphatic epoxies include, for example,3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexane carboxylate, thediepoxy spirodiacetal produced by condensation of about 2 moles of4-cyclohexenecarboxaldehyde with pentaerythritol followed by epoxidationof the double bonds, bis(3,4-epoxycyclohexylmethyl)adipate,bis(3,4-epoxycyclohexyl)adipate and vinylcyclohexenedioxide[4-(1,2-epoxyethyl)-1,2-epoxycyclohexane]. Cycloaliphatic epoxiesinclude compounds of the structures and formulas of:

Commercial examples of preferred epoxy resins include, for example,EPON® Resins DPL-862, 828, 826, 825, 1001, 1002, EPONEX® Resin 1510,HELOXY® Modifiers 32, 62, 63, 64, 65, 67, 68, 71, 107, 116, EPON® ResinDPS155, EPON® Resin HPT 1050 and CARDURA® Resin E-10 all available fromMomentive Specialty Chemicals of Columbus Ohio, and Epoxy ResinsERL-4221, -4289, -4299, -4234 and -4206 available from Union Carbide.

The reaction of the amidoamine composition with the epoxy component asdescribed above form an epoxy functional surfactant. For in-situ epoxyfunctional surfactant formation, such as in an excess of epoxy componentor in an aqueous dispersion, the epoxy functional surfactant maycomprise from about 1 wt. % to about 20 wt. %, such as from about 1 wt.% to about 10 wt. %, for example from about 1 wt. % to about 4 wt. % ofthe resulting composition.

In one embodiment of the epoxy functional surfactant, the surfactant mayhave the formula:

and m may be from 1 to 11, n may be from 1 to 3, q may be from 0 to 8,such as from 0 to 4, and p may be from about 18 to about 500. X may be ahydrogen atom, a methyl substituent, an ethyl substituent, ahydroxymethyl substituent group, subsets thereof, or combinationsthereof. Each Y may be a hydrogen atom, a methyl substituent, an ethylsubstituent, a hydroxymethyl substituent group, subsets thereof, orcombinations thereof. R₁₇ may be an alkyl group, an aryl group, an acylgroup, and subsets and combinations thereof. R₁₇ may further comprisefrom 1 to 50 carbons, and may further include oxygen, nitrogen, andsulphur atoms.

The epoxy functional surfactant may have the formula:

For repeating units, m may be from 1 to 3, n may be 1.2, q may be from1.9 to 2.3, and p may be from about 81 to about 210. X may be a hydrogenatom or a methyl substituent group. Each Y may be a hydrogen atom or amethyl substituent group. R₁₇ may be a tertiary acyl group.

The epoxy functional surfactant may be converted to an amine functionalcompound. The amine functional compound may be used as a curing agentfor an epoxy composition or as a surfactant for an amine polymercomposition. The curing agent as described herein can be produced byreacting the epoxy functional surfactants described herein and at leastone amine component, such as an amine component, as described herein.

The at least one amine component may include a polyamine. The polyaminemay have at least one primary amine group and at least one secondaryamine group. A non-limiting example of a polyamine compounds havingfirst and second amine groups is represented by the formula:H₂N—R₁₆—[NH—R₁₆]_(n)—NH₂  (V), and

For repeating units, n may be an average of integers between 1 and 10,preferably between 1 and 4, and R₁₆ is a divalent branched or unbranchedhydrocarbon radical having from 1 to 24 carbon atoms, one or more arylor alkylaryl groups, or one or more alicyclic groups, provided that theprimary polyamine compound has a total of from 2 to 18 carbon atoms.Preferably, R₁₆ is a lower alkylene radical having from 1 to 10, such asfrom 2 to 6, carbon atoms.

Examples of the polyamine compounds include ethylene polyamines,butylene polyamines, propylene polyamines, pentylene polyamines,hexylene polyamines, heptylene polyamines, and combinations thereof. Thehigher homologs of such amines and related aminoalkyl-substitutedpiperazines are also included. Specific examples of polyamines include1,2-diaminoethane, tris(2-aminoethyl)-amine, 1,2- and1,3-diaminopropane, 1,2- and 1,4-butanediamine,2-methyl-1,5-pentanediamine, 1,6-hexanediamine, 1,10-decanediamine,1,8-octanediamine, 1,4,7-triazaheptane, 1,4,7,10-tetraazadecane,1,9,17-triazaheptadecane, 2,5,8-trimethyl-1,4,7,10-tetraazadecane,1,4,7,10,13-pentaazamidecane, 1,4,7,10,13,16-hexaazahexadecane,1,5,9-triazanonane, 1,3- and 1,4-bis(aminomethyl)benzene,4,4′-diaminodiphenylmethane, 2,4-diamino-1-methylbenzene,2,6-diamino-1-methylbenzene, polymethylene polyphenylamine,1,2-diaminocyclohexane,1-amino-3-(aminomethyl)-3,5,5-trimethylcyclohexane,1,3-bis(aminomethyl)cyclohexane, 4,4′diaminodicyclohexylmethane, andcombinations thereof. Higher homologs, obtained by condensing two ormore of the above-illustrated alkylene amines, are also useful.

The curing agent as described herein can be produced by reacting theepoxy-functional component and at least one amine component in an activeamine hydrogen atom to epoxy group ratio of 2:1 or greater, such as fromabout 5:1 to about 30:1, or example, from about 5:1 to about 15:1,thereby producing an amine-terminated product. The curing agent asdescribed herein has an amine nitrogen equivalent weight of at least 50,preferably at least 65, such as from about 100 to about 400.

Additionally, the amine functional compound can be capped with amonoepoxy compound by reacting the compounds under conditions effectiveto react the remaining active amine hydrogen atoms with the epoxy groupseither before or after dispersion. The amine-terminated product can bereacted with a monoepoxy in a remaining active amine hydrogen atom toepoxy group ratio of 3:1 or greater, such as from about 5:1 to about10:1, for example about 8:1 to provide a capped product. The reaction istypically carried out at a temperature within the range from about 50°C. to about 100° C. for a time effective to produce the reactionproducts. Generally, the reaction mixture is heated until the amineequivalents consumed are equal to the epoxy equivalents (essentially allthe epoxy groups are consumed).

In one embodiment of the amine functional compound, the amine functionalcompound may have the following formula and m may be from 1 to 11, n maybe from 1 to 2, q may be from 0 to 8, and p may be from about 45 toabout 500:

X may be a hydrogen atom, a methyl substituent, an ethyl substituent, ahydroxymethyl substituent group, subsets thereof, or combinationsthereof. Each Y may be a hydrogen atom, a methyl substituent, an ethylsubstituent, a hydroxymethyl substituent group, subsets thereof, orcombinations thereof. R₁₇ may be an alkyl group, an aryl group, an acylgroup, and subsets and combinations thereof. R₁₇ may further comprisefrom 1 to 50 carbons, and may further include oxygen, nitrogen, andsulphur atoms.

Additionally, a monoepoxy compound may be introduced concurrently orsequentially with the polyamine to further react any pending substituentgroups to form the amine functional compound. The monoepoxy compound maybe any of the monoepoxy compounds as described herein. Specific examplesof monoepoxide capping agents include alkyl glycidyl ethers with 1-18linear carbon atoms in the alkyl chain such as butyl glycidyl ether or amixture of C₈-C₁₄ alkyl, glycidyl ethers, cresyl glycidyl ether, phenylglycidyl ether, nonylphenylglycidyl ether, p-tert-butylphenyl glycidylether, 2-ethylhexyl glycidyl ether, the glycidyl ester of neodecanoicacid, and combinations thereof.

Further, the curing agent as described herein can be dispersed in anaqueous solution. The dispersion may contain water and the curing agentas described herein. Such composition can be provided by mixing thewater in the curing agent as described herein before capping or aftercapping with or without the presence of a surfactant. Any conventionalsurfactant useful for emulsification or dispersion of curing agents inaqueous solutions can be used. However, the curing agents as describedherein are self-emulsifiable and do not need any additionalsurfactant(s) to provide the aqueous curing agent solution, emulsion ordispersion.

The amine functional compound, also referred to as an amine functionaladducted polymer, may be dispersed in water to give a white dispersionwith an average micron particle size diameter of Dv from about 0.2 toabout 1, for example, about 0.516, and Sa from about 0.2 to about 0.7,for example, about 0.423. The non volatile content of this dispersionmay be from about 50% to about 55%, for example, about 51.6% and the nonvolatile amine polymer amine value may be from about 225 to about 275,for example, about 257. This amine functional polymer dispersion may beused in combination with an epoxy dispersion as described herein to makethe high performance primer paint, such as described in Example 18.

The curing agent as described herein can be useful to cure a liquid or asolid epoxy resin, neat, in organic solvents or in water. Any epoxyresin described herein to produce the curing agent as described hereincan be cured by the curing agent as described herein. The curing agentcan be useful for ambient coating applications as well as bake coatingapplications. The cure temperature can vary depending on theapplication, typically in the range of about 5° C. to about 200° C.

These curing agents as described herein can be used to effectively curean aqueous epoxy resin system. Preferred examples of the aqueous epoxyresins are bisphenol-A based epoxy resins having from 350 to about10,000 molecular weight non-ionically dispersed in water with or withoutglycol ether co-solvents. Commercial examples of the aqueous epoxyresins include, for example, EPI-REZ™ Resin 3520, 3522, 3540 and 5522available from Momentive Specialty Chemicals, Inc. The curing agents asdescribed herein are compatible with aqueous dispersions without usingacid salts. These curable systems contain, water, one or more epoxyresins and one or more curing agents as described herein. These aqueouscurable epoxy resin systems can be cured at room temperature or atelevated temperatures or further catalyzed with a commercially availabletertiary amine accelerator, such as 2,4,6-tris(dimethylaminomethylphenol) or other phenols to cure at lower temperatures. Examples of suchmaterials are EPI-KURE™ Curing Agent 3253 from Momentive SpecialtyChemicals, Inc. or DMP-30 from Rohm and Haas. These low temperaturestypically range from about 5° C. to about 20° C. For the aqueous epoxyresin systems, the typical cure temperature with or without anaccelerator ranges from about 5° C. to about 200° C. Typically thesecuring agents are used to formulate thermoset coatings that have goodcorrosion protection of the coated substrate.

Aqueous Epoxy Resin Dispersions

An aqueous epoxy dispersion may include water, at least one epoxy resinas described herein, and the polyamidoamine functionalizedpolyoxyalkylene prosurfactant, which prosurfactant may either be epoxyfunctionalized in situ with the at least one epoxy resin and may beepoxy functionalized prior to contacting the at least one epoxy resin ofthe dispersion.

The aqueous epoxy resin dispersions formed herein as described aboveexhibited several improved properties over prior art dispersions. Oneimproved property is improved shelf stability as demonstrated by theimproved stability of the epoxy content, improved stability of the pH,and improved stability of viscosity.

In one aspect, an improved or equivalent viscosity over time wasobserved for the blend based surfactants herein used to form the epoxyresin dispersions described herein as compared to the non-blend priorart compositions. In one example, an aqueous epoxy resin dispersionformed from the co-amidification of acid terminated polyoxyalkylenepolyol-containing composition of a 55:45 blend of 4000 Mw/8000 Mwmolecular weight polyoxyethylene glycol components as formed in Example10 below was observed to have a viscosity of less than 1700 cps after 8months, less than 1800 cps after 10 months, and less than 1900 cps after15 months of storage. In contrast, 4000 MW polyoxyethylene glycol basedcompositions and 4600 MW polyoxyethylene glycol based compositions eachexhibited viscosities of greater than 4,000 cps at 8 months.

The aqueous dispersions formed herein were observed to have a changefrom about 0 to about 3 pH units at a period of time to double viscosityor exceed 6000 cps. Further examples of these improvements are shown inthe examples and tables described herein.

In one aspect, the average particle size in the aqueous epoxy resindispersions formed herein as described herein is on the order of lessthan 1.50 μm, such as from about 0.2 to about 1.2 μm, for example, fromabout 0.65 to about 0.87 μm in size and comparable with prior art fromabout 0.74 to 0.88 in size. It is desirable to use as small a particlesize as possible at as high an epoxy polymer content as possible toobtain improved economics and improved coalescence, thereby obtainingoptimum film mechanical properties and chemical properties.

In a typical aqueous dispersion as described herein useful for coatingapplications, the amount of the epoxy resin component, which includesthe epoxy functional surfactant, (also known as the solids content ornon-volatile content) may be from about 20 to about 75 percent byweight, preferably from about 55 to about 65 percent by weight, based onthe total dispersion. Generally, water and an epoxy resin having afunctionality of greater than 0.8 epoxide group per molecule are mixedunder conditions effective to provide an oil-in-water emulsion in thepresence of an epoxy-functional surfactant mentioned above in an amountranging from about 1 wt % to about 6 wt %, such as from about 2 wt % toabout 5 wt %, for example, from about 3.5 wt % to less than 4.5 wt %,based on the weight of solids. Given that the efficiency of the epoxyfunctional surfactant as described herein is increased, the amountrequired to disperse the epoxy resin is reduced.

Identifying the epoxy resin separately from the epoxy functionalsurfactant is for convenience only since the epoxy functional surfactantmay be made in situ in the epoxy resin. The dispersions can be made byadding the surfactant and water to the epoxy resin to be dispersed or byproducing the surfactant “in-situ” as described above. These dispersionscan also be made by adding the epoxy resin to the amidoamine compositionand water. The surfactant can be produced in-situ by addingpolyamidoamine functionalized polyoxyalkylene prosurfactant to the epoxyresin at an effective temperature to react the amidoamine and epoxyresin, or by adding the polyamidoamine functionalized polyoxyalkyleneprosurfactant to a difunctional epoxy resin and dihydric phenol beforeor during the advancement reaction as described above.

One or more epoxy-functional amidoamine prosurfactants can be used.Optionally, a co-surfactant can be used along with the epoxy functionalsurfactant. Optionally, the dispersion also contains acetone. In oneembodiment, the dispersion contains acetone and at least onenon-volatile hydrophobic liquid resin or resin modifier. Acetone may bepresent in an amount of about 0.5 wt. % or greater, more preferably inan amount from about 1 wt. % to about 3 wt. %, such as about 1.5 wt. %.

Useful coating compositions can be obtained by mixing anamine-functional epoxy resin curing agent with the aqueous epoxy resindispersion mentioned above. The aqueous epoxy resin dispersions andcuring agents described above can serve as components of paints andcoatings for application to substrates such as, for example, metal andcementitious structures. To force the coating composition cure tocompletion, the coatings obtainable from these dispersions may also beheated for about 30 to about 120 minutes at an elevated temperature,preferably within the range of about 50° C. to about 120° C.

To prepare such paints and coatings, the aqueous epoxy resin dispersionsand/or curing agents are blended with primary, extender andanti-corrosive pigments, and optionally, additives such as surfactants,antifoam agents, rheology modifiers and mar and slip reagents. The epoxyresin coating composition as described herein may include otheradditives, such as elastomers, stabilizers, extenders, plasticizers,pigment pastes, antioxidants, leveling or thickening agents, and/orco-solvents, wetting agents, co-surfactants, reactive diluents, fillers,catalysts, and combinations thereof. The selection and amount of thesepigments and additives depends on the intended application of the paintand is generally recognized by those skilled in the art.

The reactive diluent can be any non-volatile, hydrophobic compound whichis liquid and flowable at room temperature, whether neat or in ahydrophobic solvent such as xylene or butanol. A substance isnon-volatile when it meets the definition according to ASTM D 2369-93 orASTM D 3960-93. For a coating composition, the reactive diluent (alsoknown as a hydrophobic liquid resin or resin modifier) must becompatible (e.g. does not detract from corrosion resistance, or highgloss, etc.) with the curing agents in the coating composition, forexample, such as amine curing agents.

A reactive diluent may be present in an amount up to about 25 wt. %,such as from about 1 to about 10 wt. % based on the total amount ofcomponents. Preferable reactive diluents include, for example, aliphaticmonoglycidyl ethers, urea formaldehyde resins or aliphatic monoglycidylesters. Preferable monoepoxide diluents are those which contain awater-immiscible glycidated C₈₋₂₀ aliphatic alcohol, C₁₋₁₈ alkylphenolglycidyl ether, or glycidated tertiary carboxylic acid. The monoepoxidecomponent can contain alicyclic and aromatic structures, as well ashalogen, sulfur, phosphorus, and other such heteroatoms. Reactivediluents can be, for example, epoxidized unsaturated hydrocarbons suchas decene and cyclohexene oxides; glycidyl ethers of monohydric alcoholssuch as 2-ethylhexanol, dodecanol and eicosanol; glycidyl esters ofmonocarboxylic acids such as hexanoic acid; acetals of glycidaldehyde;and the like. The preferred reactive diluent is the glycidyl ether ofmonohydric C₈₋₁₄ aliphatic alcohols. Reactive diluents are commerciallyavailable as HELOXY™ 7 Modifier (C₈-C₁₀ alkyl glycidyl ether), HELOXY™ 9Modifier (C₁₀₋₁₁ alkyl glycidyl ether) from Momentive SpecialtyChemicals and CYMEL UF™ 216-10 Resin (alkylated urea formaldehyde highsolids solution) from Cytec Industries Inc. The aqueous dispersion mayalso contain a monoepoxide diluent as a reactive diluent.

Examples of primary pigments include rutile titanium dioxide, such asKRONOS® 2160 (Kronos, Inc.) and TI-Pure® R-960 from Du Pont, bufftitanium dioxide, red iron oxide, yellow iron oxide and carbon black.Examples of extender pigments include calcium metasilicate, such as 10ESWOLLASTOKUP® (NYCO Minerals, Inc.), barium sulfate, such as SPARMITE®(Harcros Pigments, Inc.) and aluminum silicate, such as ASP® 170(Englehard Corp.). Examples of anticorrosive pigments include calciumstrontium phosphosilicate, such as HALOX SW111 (Halox Pigments), zincion modified aluminum triphosphate, such as K-WHITE® 84 (Tayca Corp.)and basic aluminum zinc phosphate hydrate, such as HEUCOPHOS® ZPA (HeucoTech, Ltd.).

Additional surfactants can be included in waterborne epoxy paints andcoatings to improve both pigment and substrate wetting. Such surfactantsare typically non-ionic, examples of which include TRITON® X-100 andTRITON X-405 (Dow Chemical Company), and SURFYNOL® 104 (Air Products andChemicals).

Anti-foam agents and defoamers suppress foam generation duringmanufacture of the paint or coating. Useful defoamers include DREWPLUS®L-475 (Drew Industrial Div.), DEE FO® PF-4 Concentrate (Ultra Additives)and BYK® 033 (BYK-Chemie).

Rheological additives are employed to obtain proper applicationproperties. There are three types of additives that provide the desiredthickening and shear thinning required for waterborne epoxy coatings;namely, hydroxyethylcellulose, organically modified hectorite clays andassociative thickeners. NATROSOL® 250 MBR and NATROSOL Plus (Aqualon)are examples of modified hydroxyethyl-cellulosics and BENTONE® LT(RHEOX, Inc.) is representative of a hectorite clay. Optiflo™ (SouthernClay) is a useful associative thickener.

Mar and slip agents improve early resistance to abrasion from scrubbingor light foot traffic. Polydimethylsiloxanes and polyoxyethylene waxesare used in this regard. An example of a commercially available wax slipagent is MICHEM LUBE® 182 (MICHELMAN, INC.).

The curable paint and coating compositions can be applied to a substrateby brush, spray, or rollers. The aqueous dispersions of the instantinvention can also be used as components of adhesives and fiber sizing.

Other uses for the pro-surfactants, surfactants, aqueous dispersion andcuring agents as described herein may include moisture control membranesfor curing concrete as well as thin adhesives for multi-layered metallaminates.

Additionally, the epoxy resin curing agent can be any curing agenteffective to cure (or crosslink) the epoxy resin dispersed in theaqueous solution including the curing agents made from the epoxyfunctional amidoamine prosurfactant described herein. The curing agentsare generally water compatible (i.e., dilutable and/or dispersable).

Other suitable curing agents or co-curing agents for use with thedispersions include those typically employed with epoxy resins, such asaliphatic, arylaliphatic and aromatic amines, polyamides, amidoaminesand epoxy-amine adducts, melamine formaldehyde resins and phenolicformaldehyde resins. The curing agents exhibit varying levels ofcompatibility with water, depending upon the nature of the startingmaterials employed for their preparation.

Preferably, for curing at room temperature or lower temperatures, theother suitable curing agents or co-curing agents may have an epoxideequivalent to amine hydrogen equivalent combining ratio of from about1:0.75 to about 1:1.5. Such other suitable curing agents or co-curingagents may include polyalkylene amine curing agents are those which aresoluble or dispersible in water and which contain more than 2 activehydrogen atoms per molecule such as diethylenetriamine,triethylenetetramine, tetraethylenepentamine, etc. Examples include1,6-hexanediamine, 1,3-pentanediamine,2,2(4),4-trimethyl-1,6-hexanediamine, bis(3-aminopropyl)piperazine,N-aminoethylpiperazine, N,N′-bis(3-aminopropyl)ethylenediamine,2,4(6)-toluenediamine and also cycloaliphatic amines such as1,2-diaminocyclohexane, 1,4-diamino-2,5-diethylcyclohexane,1,2-diamino-4-ethylcyclohexane, 1,2-diamino-4-cyclohexylcyclohexane,isophoronediamine, norbornanediamine, 4,4′-diaminodicyclohexylmethane,1,1-bis(4-aminocyclohexyl)ethane, 2,2-bis(4-aminocyclohexyl)propane,3,3′-dimethyl-4,4′-diaminodicyclohexylmethane,3-amino-1-(4-aminocyclohexyl)propane, 1,3- and1,4-bis(aminomethyl)cyclohexane, and combinations thereof. Asaraliphatic amines, in particular those amines are employed in which theamino groups are present on the aliphatic radical, for example, m- andp-xylylenediamine or their hydrogenation products. The amines may beused alone or as mixtures.

For higher temperature cure applications, aminoplast resins can be usedas curing agents for epoxy resins having a high equivalent weight, e.g.greater than 700. Generally, from about 5 to about 40, such as fromabout 10 to about 30, for example, about 30 weight percent of aminoplastresins, based on the combined weight of the epoxy resin and aminoplastresin, is used. Suitable aminoplast resins are the reaction products ofureas and melamines with aldehydes further etherified in some cases withan alcohol. Examples of aminoplast resin components are urea, ethyleneurea, thiourea, melamine, benzoguanamine and acetoguanamine. Examples ofaldehydes include formaldehyde, acetaldehyde and propionaldehyde. Theaminoplast resins can be used in the alkylol form but, preferably, areutilized in the ether form wherein the etherifying agent is a monohydricalcohol containing from 1 to 8 carbon atoms. Examples of suitableaminoplast resins are methylol urea, dimethoxymethylol urea, butylatedpolymeric urea-formaldehyde resins, hexakis(methoxymethyl)melamine,methylated polymeric melamine-formaldehyde resins and butylatedpolymeric melamine-formaldehyde resins.

Commercial examples of water-compatible curing agents include EPI-CURE™8540, 8537, 8290 and 6870 Curing Agents (available from MomentiveSpecialty Chemicals), ANQUAMINE 401, Casamid 360 and 362 curing agents(Air Products); Hardener HZ350, Hardeners 92-113 and 92-116 (Huntsman);BECKOPDX EH659W, EH623W, VEH2133W curing agents (Cytec) and EPOTUF37-680 and 37-681 curing agents (Reichhold Chemical Co.).

The curable epoxy resin composition can be cured at a temperature withinthe range of from about 5° C. to about 200° C., such as from 20° C. toabout 175° C., for a time effective to cure the epoxy resin.

EXAMPLES

The following examples are provided to illustrate certain embodiments asdescribed herein. The examples are not intended to limit the scope ofthe application and they should not be so interpreted. Amounts are inweight or volume parts or in weight or volume percentages unlessotherwise indicated.

Testing Methods

Viscosities were determined on the obtained emulsion or dispersion bymeans of a Brookfield Synchro Lectric Viscometer from BrookfieldEngineering Laboratories.

The determination of emulsion and dispersion particle sizes wasaccomplished with a Brookhaven Bi-DCP Particle Sizer from BrookhavenInstruments Corporation and Coulter LS230 unless otherwise specified. Dnis number average particle size diameter, Dw is mass average particlesize diameter, Dv is the volume average size diameter, and Sa is surfacearea average particle size diameter. All particle size data is reportedin micrometers, μm.

Amine values are reported as milligrams of KOH that is equivalent tobasic nitrogen content of an one gram sample, determined by acid-basetitration, ASTM D2896 test process.

The acid equivalent weight/carboxyl equivalent weight was determined bythe ASTM D1639 testing procedure.

The amine nitrogen equivalent weight was theoretically determined bybatch calculations using reactant equivalent weights and batch massbalance.

Epoxy equivalent weights were determined by ASTM D1652 and D4142 testingprocedures.

Examples of compositions and processes to form the compositions arepresented as follows.

EXAMPLE 1A is a comparative example of a state of the art compositionand process of the oxidation of polyoxyethylene glycol (PEG) having 4600number average molecular weight and a high carboxyl level (U.S. Pat. No.6,956,086 B2 Example 1).

To a stainless steel reactor with a capacity of approximately 1150liters, 601.5 Kg of PEG 4600 and 45.4 Kg of water were added to form amixture. The mixture was heated to 60° C. and stirred to dissolve thePEG. Then, 5.41 Kg of 4-hydroxy-2,2,6,6,tetramethylpiperidine-1-oxylfree radical (4-hydroxy TEMPO) and a mixture of 7.14 Kg of 67% nitricacid and 21.9 Kg of water were charged to the reactor while stirring.The reactor vent was then closed and oxygen was added to the reactor.Sufficient oxygen was added to bring and keep the reactor at an oxygenpressure of 25 psig (172 kPa) in addition to the air which was in thereactor before oxygen addition. The reactor was kept at 57-63° C. whilestirring for 4 hours as additional oxygen was added from the cylinderthrough a regulator set to keep the added oxygen pressure at 172 kPa. Atthis point, the cylinder pressure had dropped by 1975 psig (13.62 MPa),indicating that 8.38 Kg of oxygen had been transferred from the cylinderto the reactor. The oxygen flow was then turned off and the reaction wascontinued for two additional hours at this temperature while stirring inorder to consume most of the oxygen in the headspace of the reactor.

At the end of this time, the pressure of added oxygen in the reactorheadspace had dropped to 9.6 psig (66 kPa) and the rate of oxygenconsumption had become very slow. The remaining oxygen was vented andvacuum was applied to the reactor to bring the absolute pressure down to13.5 kPa. The reactor temperature was increased to 93° C. to distill thewater and remaining nitric acid into the overhead accumulator.Distillation was continued for 1.5 hours. Vacuum was broken to samplethe product for acid equivalent weight. The acid equivalent weight was2382, corresponding to 93% oxidation of the alcohol end groups. Theoverhead accumulator was drained. This oxidized PEG was used to make thecomparative, state of the art, polyamidoamine prosurfactant in Example4.

Example 1B is an example of the oxidation of polyoxyethylene glycol(PEG) having 4600 number average molecular weight to a high carboxyllevel.

To a stainless steel reactor with a capacity of approximately 57 liters30 Kg of PEG 4600 (with a hydroxyl equivalent weight of 2300) and 2.53Kg of water were added to form a mixture. The mixture was heated to 60°C. and stirred to dissolve the PEG. Then, 0.54 Kg of 4-hydroxy TEMPO(dissolved in 1.08 Kg of water) and a mixture of 0.18 Kg of 67% nitricacid and 0.45 Kg of water were charged to the reactor while stirring.The reactor vent was then closed and oxygen was added to the reactorfrom a cylinder with a regulator. Sufficient oxygen was added to bringand keep the reactor at an oxygen pressure of 25 psig (170 kPa) inaddition to the air which was in the reactor before oxygen addition. Thereactor was kept at 60° C. while stirring for 9.5 hours as additionaloxygen was added from the cylinder through a regulator set to keep theadded oxygen pressure at 170 kPa. Samples were periodically withdrawnfrom the reactor and the carboxyl equivalent weight of the solidfraction (which could be used in turn to calculate the percentageoxidation) was determined on the dried sample by titration.

After 9.5 hours a final sample was taken and the flow of oxygen to thereactor was stopped while the sample was being analyzed. Titration ofthe dried sample showed a carboxyl equivalent weight of 2440,corresponding to conversion of 94.3% of the hydroxyl groups to carboxyl.When the analytical result was obtained, the oxygen in the reactor wasvented and the reactor was purged with nitrogen.

Then, the reactor temperature was increased to approximately 105° C. asthe reactor pressure was reduced to approximately 1700 Pa. Water andother volatiles were distilled from the reactor for approximately 3hours until the offtake of distillate had essentially stopped. Themolten product remaining in the reactor was then loaded out into pails.The product had an acid equivalent weight of 2410 without post-dryingand 2440 on a sample dried for 15 minutes in an air oven at 150° C. Thelatter value corresponded to an extent of oxidation of the hydroxyl endgroups to carboxyl of 94.7%.

EXAMPLE 2 is an example of the oxidation of polyoxyethylene glycol(PEG), 4000 number average molecular weight, to a high carboxyl level.

To a stainless steel reactor with a capacity of approximately 57 liters30 Kg of PEG 4000 (with a hydroxyl equivalent weight of 2085) and 2.95Kg of water were added to form a mixture. The mixture was heated to 60°C. and stirred to dissolve the PEG. Then, 0.57 Kg of 4-hydroxy TEMPO(dissolved in 1.06 Kg of water) and a mixture of 0.18 Kg of 67% nitricacid and 0.45 Kg of water were charged to the reactor while stirring.The reactor vent was then closed and oxygen was added to the reactorfrom a cylinder with a regulator. Sufficient oxygen was added to bringand keep the reactor at an oxygen pressure of 35 psig (240 kPa) inaddition to the air which was in the reactor before oxygen addition. Thereactor was kept at 56-61° C. while stirring for 5.5 hours as additionaloxygen was added from the cylinder through a regulator set to keep theadded oxygen pressure at 240 kPa. Samples were periodically withdrawnfrom the reactor and the carboxyl equivalent weight of the solidfraction (which could be used in turn to calculate the percentageoxidation) was determined on the dried sample by titration.

After 5.25 hours the carboxyl equivalent weight of the solid fractionwas 7620 which corresponded to conversion of 27.4% of the hydroxylgroups to carboxyl. To raise the oxidation rate, the oxygen pressure wasincreased to 50 psig (345 kPa above the pressure of the starting air)after 5.5 hours. Reaction was continued at the increased pressure forone additional hour before the reactor was vented and the reaction wasstopped for the evening.

Then, the reactor was pressurized with oxygen to 50 psig (345 kPa) aboveatmospheric and reheated to 56-61° C. The mixture was held at thistemperature and oxygen pressure, while stirring, for 4.5 additionalhours. At the end of this time a sample was taken and the flow of oxygento the reactor was stopped while the sample was being analyzed.Titration of the dried sample showed a carboxyl equivalent weight of2597, corresponding to conversion of 80.3% of the hydroxyl groups tocarboxyl. When the analytical result was obtained, the oxygen in thereactor was vented and the reactor was purged with nitrogen. The productwas then diluted with water to a solids content of 52% (to retardcrystallization of the oxidized PEG from solution) and loaded from thereactor into pails. Titration of a dried sample of the final productshowed a carboxyl equivalent weight of 2416, corresponding to conversionof 86.3% of the hydroxyl groups to carboxyl. This oxidized PEG was usedto make the polyamidoamine prosurfactants described in Example 5 and ina blend in Example 7.

Example 3 is an example of the oxidation of polyoxyethylene glycol(PEG), 8000 number average molecular weight, to a high carboxyl level.

To a stainless steel reactor with a capacity of approximately 57 liters30 Kg of PEG 8000 (with a hydroxyl equivalent weight of 4057) and 2.95Kg of water were added to form a mixture. The mixture was heated to 60°C. and stirred to dissolve the PEG. Then, as in Example 2, 0.57 Kg of4-hydroxy TEMPO (dissolved in 1.06 Kg of water) and a mixture of 0.18 Kgof 67% nitric acid and 0.45 Kg of water were charged to the reactorwhile stirring. The reactor vent was then closed and oxygen was added tothe reactor from a cylinder with a regulator. Sufficient oxygen wasadded to bring and keep the reactor at an oxygen pressure of 50 psig(345 kPa) in addition to the air which was in the reactor before oxygenaddition. The reactor was kept at 56-61° C. while stirring for 5.8 hoursas additional oxygen was added from the cylinder through a regulator setto keep the added oxygen pressure at 345 kPa. Samples were periodicallywithdrawn from the reactor and the carboxyl equivalent weight of thesolid fraction (which could be used in turn to calculate the percentageoxidation) was determined on the dried sample by titration. After 5hours the carboxyl equivalent weight of the solid fraction was 7114which corresponded to conversion of 57.0% of the hydroxyl groups tocarboxyl. After 5.8 hours the reactor was vented and the reaction wasstopped for the evening.

Then, a sample was taken again and the carboxyl equivalent weight of thesolid fraction was 6158 which corresponded to conversion of 65.9% of thehydroxyl groups to carboxyl. The reactor was pressurized with oxygen to50 psig (345 kPa) above atmospheric and reheated to 56-61° C. Themixture was held at this temperature and oxygen pressure, whilestirring, for 2 additional hours. At the end of this time a sample wastaken and the flow of oxygen to the reactor was stopped while the samplewas being analyzed. Titration of the dried sample showed a carboxylequivalent weight of 4995, corresponding to conversion of 81.2% of thehydroxyl groups to carboxyl. When the analytical result was obtained,the oxygen in the reactor was vented and the reactor was purged withnitrogen. The product was then diluted with water to a solids content of52% (to retard crystallization of the oxidized PEG from solution) andloaded from the reactor into pails. Titration of a dried sample of thefinal product showed a carboxyl equivalent weight of 4940, correspondingto conversion of 82.1% of the hydroxyl groups to carboxyl. This oxidizedPEG was used to make the polyamidoamine prosurfactants in Example 6 andin a blend in Example 7.

EXAMPLE 4A is a comparative example of the preparation of a state of theart amidoamine prosurfactant composition using the product of Example 1Aas the starting raw material (U.S. Pat. No. 6,956,086 B2 Example 1).

The reactor contents of Example 1A were then cooled to 68° C. and 123.1Kg of 2-methyl-1,5-pentanediamine, Dytek A, were then charged to thereactor. The reactor temperature was raised to 202° C. over a period of2.5 hours as a mixture of water and some of the diamine was allowed todistill at atmospheric pressure. When the reactor contents had reachedthis temperature, the overhead accumulator was drained and vacuum wasapplied to strip the remaining diamine. After 2.75 hours, the reactorpressure was 3 kPa, the temperature was 209° C. and a nitrogen spargewas applied to promote the stripping of excess diamine. Stripping wascontinued for 4.5 additional hours with vacuum and nitrogen. Vacuum wasbroken and the reactor contents were sampled; the amine nitrogenequivalent weight was 2905.

The reactor was then cooled to 104° C. and charged with 317.6 Kg ofwater to dissolve the product, followed by 38.1 Kg of CARDURA E-10 (aglycidyl ester of a C₁₀ tertiary carboxylic acid). The mixture wasstirred at 93° C. for one hour to react the epoxy groups of the CARDURAE-10 with the amine groups of the oxidized polyoxyethyleneglycol-diamine condensate. Solids content was measured and 63.5 Kg ofadditional water was added to adjust solids concentration to the desiredlevel. The product was loaded out into drums.

The final product had a solids concentration of 63.7% and an aminenitrogen equivalent weight of 3281 (solids basis). Gel permeation (sizeexclusion) chromatography of the product (polyoxyethylene glycolcalibration) showed a low molecular weight peak at a peak molecularweight of 4590 (64.2% of area) and a high molecular weight peak at apeak molecular weight of 9268 (31.4% of area, probably corresponding tocoupled material). The remaining area corresponded to material of a fewhundred molecular weight. No particular broadening of the lowermolecular weight peak into the low molecular weight region,corresponding to chain scission, was observed. The total mixture had anumber average molecular weight of 3758 and a weight average molecularweight of 6260. The percentage of oligomeric amidoamine compoundspresent in the amidoamine composition was 31.4% based on GPC. Thepolydispersity, PD, was relatively low and the M_(z) was relatively low(Table II.).

This Example 4A prosurfactant forms an efficient in situ epoxydispersion surfactant for low viscosity and small particle size asdemonstrated by Example 8 in Tables III, IV, and V). However, as alsoshown the viscosity, the epoxy equivalent weight, and the particlediameter increase significantly with time, thus routinely providing avery limited shelf life of less than one year.

Example 4B is an example of the preparation of condensates of product ofExample 1 with alkylated 1,3-propanediamines and their aqueoussolutions.

A 1-liter, 4-neck round bottom flask was equipped with a paddle stirrer,thermocouple, distillation takeoff, and vacuum takeoff/nitrogen purge.To the flask was charged the amounts shown in Table I of the product ofExample 1B (after stripping of volatiles) and the following amines: A, aN-oleyl trimethylenediamine, B, a N-(branchedtridecyloxypropyl)trimethylenediamine, and C, aN-((octyl/decyl)oxypropyl)trimethylenediamine mixture.

The flask was purged with nitrogen and heated to 215° C. at the maximumheating rate set by the temperature controller. Water distilled from thereaction mixtures as the amide formation reaction proceeded. Thereaction mixtures were held for 1 hour at 215° C. under nitrogen atatmospheric pressure and then for 30 minutes (1 hour in the case ofmixtures 3 and 5) at this temperature at a reduced pressure of 80-160Pa. The reaction mixtures were then cooled to approximately 90° C. andwater was added to make aqueous solutions. The percentage solids and 25°C. Brookfield viscosity of the aqueous solutions were determined. Thesolutions were also analyzed by gel permeation chromatography (GPC). TheGPC chromatogram of each solution showed three peaks, with a lowmolecular weight peak at MW 1000-1200, a medium molecular weight peak atMW 4300-4600 (similar to the position of the main peak in the startingmaterial), and a high molecular weight peak at MW 9300-9800. The areapercentage of each peak was calculated and is shown in Table I below.

TABLE I Mixture# 1 2 3 4 5 Product of Example 4, 438.25 438.25 438.25438.25 438.25 acid equiv. 0.1796 0.1796 0.1796 0.1796 0.1796 Diamine A BB C C Diamine, amine nitrogen 171.94 165.76 165.76 137.5 137.5 equiv.wt. Diamine, grams 61.75 59.53 44.65 49.38 37.03 amine nitrogen equiv.0.359 0.359 0.269 0.359 0.269 Nitrogen equivalents: 2 2 1.5 2 1.5diamine/equiv acid Distillate, grams 46.6 14 14.5 Added water, grams 275275 275 275 275 Product, grams 691 690 739 719 729 Product, % solids65.34 66.64 62.11 62.72 62.07 Viscosity, Brookfield, 153 3.57 3.11 0.7760.83 25° C., Pa-s GPC, peak % area: Low 17.5 17.1 27.8 18.8 28.4 Medium69.7 69.1 54.8 66.4 53.2 High 12.8 13.9 17.5 12.8 18.4

One can see from Table I that the ether diamines B and C producedcondensates much lower in aqueous solution viscosity than that from thelong chain hydrocarbon diamine A.

EXAMPLE 5 is an example of the preparation of an amidoamineprosurfactant composition using the product of Example 2 as the startingraw material.

To a resin flask equipped with agitation, a heating mantle, a nitrogensparge and a vacuum system were added 1200.0 grams of aqueous,carboxylated polyoxyethylene oxide from Example 2. The water was removedfrom the product of Example 2 by vacuum distillation at 91° C. Then154.8 grams 2-methyl-1,5-pentanediamine (Invista Dytek A) were added tothe flask. A condenser was added to the flask to allow the contents toreflux. The mixture was heated to 181° C. and mixed at this temperaturefor 45 minutes under reflux while sparging gently with nitrogen. Vacuumand heat were applied to distill out excess Dytek A and water to formthe amidoaminified reactants. After 1 hour at 181° C. and 6.7 KPaabsolute pressure, the formed amidoamine of the carboxylatedpolyoxyethylene oxide and Dytek A had an amine nitrogen equivalentweight of 2639. The batch was then steam sparged with wet nitrogen at164° C. to raise the amine nitrogen equivalent weight to 2865. Afterallowing the batch to cool to 110° C., deionized water was added toreduce the solids to 70%. To the batch was added 34 grams CARDURA E-10(a glycidyl ester of a C₁₀ tertiary carboxylic acid) at 62° C. Afterallowing the batch to mix for 2 hours at 55-62° C., it was diluted to64.8% solids and allowed to set overnight at room temperature.

The amine nitrogen equivalent weight of the aqueous capped amidoaminepolymer was determined to be 3079. This prosurfactant was then used tomake an epoxy dispersion as shown in Example 11, which epoxy dispersionwas observed to have a low viscosity. This prosurfactant was also usedwith the prosurfactant from Example 6 to make the epoxy dispersion ofExample 9, which epoxy dispersion exhibited a better shelf stabilitycompared to the comparative “state of the art” Example 8.

EXAMPLE 6 is an example of the preparation of an amidoamineprosurfactant composition using Example 3 as the starting raw material.

To a resin flask equipped with agitation, a heating mantle, a nitrogensparge and a vacuum system were added 1500.0 grams of aqueous,carboxylated polyoxyethylene oxide from the product of Example 3. Thewater was removed from the product of Example 3 by vacuum distillationat 91° C. Then 95.3 grams 2-methyl-1,5-pentanediamine (Invista Dytek A)were added to the flask. A condenser was added to the flask to allow thecontents to reflux. The mixture was heated to 179° C. and mixed at thistemperature for 45 minutes under reflux while sparging gently withnitrogen. Vacuum and heat were applied to distill out excess Dytek A andwater to form the amidoaminified reactants. After 2.5 hours at 181° C.and 5.1 KPa absolute pressure, the formed amidoamine of the carboxylatedpolyoxyethylene oxide and Dytek A had an amine nitrogen equivalentweight of 2111. After 3 hours of continued vacuum distillation the aminenitrogen equivalent weight was 4531. The batch was then steam spargedwith wet nitrogen at 155° C. to raise the amine nitrogen equivalentweight to 5013. After allowing the batch to cool to 110° C., deionizedwater was added to reduce the solids to 70%. Then 34 grams CARDURA E-10(a glycidyl ester of a C₁₀ tertiary carboxylic acid) was added at 66° C.After allowing the batch to mix for 2 hours at 55-62° C., it was dilutedto 64.2% solids and allowed to set overnight at room temperature.

The amine nitrogen equivalent weight of the aqueous capped amidoaminepolymer was determined to be 5333. This prosurfactant was used to makean epoxy dispersion as shown in Example 12, which dispersion had a lowpH and superior epoxy content stability. This prosurfactant was alsoblended with the prosurfactant from Example 5 to form the Example 9epoxy dispersion which had improved shelf stability compared to that ofthe “state of the art” Example 8.

EXAMPLE 7 is an example of the preparation of the preferred inventionamidoamine prosurfactant composition using a blend of the products ofExample 2 and Example 3 as the starting raw materials.

To a stainless steel reactor equipped with a heating mantle, agitation,a nitrogen sparge and a vacuum system were added 2312.1 grams ofaqueous, carboxylated polyoxyethylene oxide from the product of Example2 and 1890.0 grams from the product of Example 3. The water was removedfrom this blend by vacuum distillation at up to 105° C. and 6.7 KPaabsolute pressure. Then 418.1 grams 2-methyl-1,5-pentanediamine (InvistaDytek A) were added to the batch. A condenser was added to the flask toallow the contents to reflux. The mixture was heated to 184° C. andmixed at this temperature for 45 minutes under reflux while sparginggently with nitrogen. Vacuum and heat were applied to distill out excessDytek A and water to form the amidoaminified reactants. After 4 hours at171-188° C. and 13.5 to 5.1 KPa absolute pressure, the formed amidoamineof the carboxylated polyoxyethylene oxide and Dytek A had an aminenitrogen equivalent weight of 3811. After allowing the batch to cool to110° C., deionized water was added to reduce the solids to 70%. Then97.3 grams CARDURA E-10 (a glycidyl ester of a C₁₀ tertiary carboxylicacid) was added at 66° C. After allowing the batch to mix for 2 hours at70-83° C., it was diluted to 64.3% solids.

The amine nitrogen equivalent weight of the capped amidoamine polymerwas determined to be 3750. As expected from the molecular weightdispersity DP of the blend of the PEG 4000 and PEG 8000, this Example 7coamidified blend of the oxidized respective PEG acids also has amolecular weight dispersity DP 1.2895 that is nearly the same as butslightly lower compared to that of the relevant blend of Examples 5 and6 amidoaminified prosurfactants as shown in Table II. This coamidifiedprosurfactant was also used to make the preferred invention epoxydispersion Example 9 which had lower viscosity, lower particle size andsuperior shelf stability that the state of the art examples.

EXAMPLE 8 is a comparative epoxy dispersion example involving thepreparation of the epoxy dispersion made from a prosurfactant preparedaccording to the method described in Example 4.

To a resin flask equipped with a heating mantle, an agitator, a nitrogenpurge, a vacuum system and a condenser were added 936.9 grams of EPONResin 828 and 285.1 grams bisphenol A. The batch was heated withagitation to 115° C. Then 1.0 gram of triphenylphosphine was added tothe mixture. The batch was heated with agitation to 132° C. and allowedto exotherm as high as 190° C. The batch was then held at 177° C.-190°C. for 45 minutes. The batch was then cooled to 132° C. and 99.3 gramsof propylene glycol monomethyl ether were added. The batch was refluxedand cooled to 105° C. Then 84.1 grams of Example 4A prosurfactant havinga high molecular weight content of 28.7%, 3164 equivalent weightnitrogen and 64.7% solids were added at atmospheric pressure. The batchwas allowed to cool with agitation to 99° C. over 2.5 hours. At thispoint 285.5 grams of deionized water was quickly added to the batch over5 minutes. The batch was then cooled with reduced pressure to 77° C. atwhich point the epoxy polymer and the prosurfactant epoxy formed a resinin water dispersion.

After mixing the dispersion for an additional 1.0 hrs at 44.0 KPaabsolute pressure (to cool the batch to 55° C.) the mean Sa diameter(surface area) particle size was 0.723 microns and the mean Dv (volume)particle size was 1.105 microns. At this point the batch was returned toatmospheric pressure and 13.0 grams of acetone were added to the batch.The batch was mixed for 15 minutes at 55° C. and 1.26 grams of 50%polypropylene glycol solution of dodecylbenzene sulfonic acid was addedto control the pH to near neutral. The batch was mixed an additional 15minutes and then 26.0 grams of HELOXY Modifier 8 were added over 10minutes. The batch was mixed for 20 minutes and then allowed to coolovernight. The next morning the batch was warmed with agitation over 1.0hour to 52° C. The batch was diluted with deionized water over 2 hourswhile allowing the temperature to cool to 48° C.

The batch was mixed an additional 20 minutes and then filtered throughan 80 mesh filter bag. Samples were further diluted to 55.9%, 54.2%, and51.8% non-volatiles. The batch Brookfield RVDVI viscosities measured thesame day they were diluted were 16,740 cP, 7,040 cP, and 2,600 cPrespectively at measured with spindle 5 and 20 rpm at 25° C. The initialviscosities (after 1 day at 49° C./2 days at 25° C. to allow fordeairing and pH equilibration) were 15,560 cP, 5,900 cP and 1,620 cP atthe respective % solids. The particle size of this final epoxydispersion was Sa 0.743 and Dv 0.942 microns. The epoxide equivalentweight of the resin content was 504. The pH of the batch after 1 day at49° C. plus 1 day at 25° C. was 8.60. As shown in Table III, this epoxydispersion made with the Example 4, standard prosurfactant, had a lowparticle size, a moderate initial viscosity and a relatively high pH.The high pH contributed to the relatively fast rates of viscosity andepoxy equivalent weight increases as shown in Table III. Thus theincrease in viscosity and epoxy equivalent weight limits the statedshelf life to less than one year.

The structure for the state of the art surfactant of Example 8 is thefollowing structure where n is 1.2.

Example 9A is an example of the preparation of the epoxy dispersion madefrom a 55:45 Ratio Blend of prosurfactants Example 5 and Example 6respectively.

To a resin flask equipped with a heating mantle, an agitator, a nitrogenpurge, a vacuum system and a condenser were added 933.3 grams of EPONResin 828 and 289.5 grams bisphenol A. The batch was heated withagitation to 105° C. Then 1.0 gram of triphenylphosphine was added tothe mixture. The batch was heated with agitation to 132° C. and allowedto exotherm as high as 190° C. The batch was then held at 177° C.-190°C. for 45 minutes. The batch was then cooled to 136° C. and 99.3 gramsof propylene glycol monomethyl ether were added. The batch was refluxedand cooled to 105° C. Then 47.0 grams of Example 5 and 38.4 grams ofExample 6 (85.4 g total) were added at atmospheric pressure. The batchwas allowed to cool with agitation to 99° C. over 2.0 hours. At thispoint 284.6 grams of deionized water was quickly added to the batch over5 minutes. The batch was then cooled with reduced pressure to 77° C. atwhich point the epoxy polymer and the prosurfactant epoxy formed a resinin water dispersion.

After mixing the dispersion for an additional 2.5 hours at 44.0 KPaabsolute pressure (to cool the batch to 55° C.) the mean Sa diameter(surface area) particle size was 0.875 microns and the mean Dv (volume)particle size was 1.345. At this point the batch was returned toatmospheric pressure and 13.0 grams of acetone were added to the batch.The batch was mixed for 5 minutes at 55° C. and 1.26 grams of 50%polypropylene glycol solution of dodecyl benzene sulfonic acid was addedto control the pH to near neutral. The batch was mixed an additional 10minutes and then 26.0 grams of HELOXY Modifier 8 were added over 10minutes. The batch was mixed for 20 minutes and then allowed to coolovernight. The next morning the batch was warmed with agitation over 1.0hour to 54° C. The batch was diluted with deionized water over 2 hourswhile allowing the temperature to cool to 50° C.

The batch was mixed an additional 20 minutes and then filtered throughan 80 mesh filter bag. Samples were further diluted to 55.7%, 54.5%, and52.1% non-volatiles. The fresh viscosities (as measured in Example 8)were 15,160 cP, 6,160 cP and 2,020 cP respectively at 25° C. The initialviscosities (after 1 day at 49° C./2 days at 25° C.) measured 15,960 cP,5,100 cP and 1,480 cP. The particle size of this final epoxy dispersionwas Sa 0.862 and Dv 1.428 microns. The epoxide equivalent weight of theresin content was 506. The pH of the batch after 1 day at 49° C. plus 2days at 25° C. was 8.18. As shown in Table III, the pH of thisdispersion and the resulting viscosity and epoxy equivalent weight rateof increase were better than the standard dispersion Example 8. Thisdispersion also had better shelf stability than both Examples 11 and 12as shown in Table IV.

Example 9B is an example of the preparation of the epoxy dispersion madefrom an 85:15 ratio blend of prosurfactants Example 5 and Example 6respectively. This epoxy dispersion was made by following the sameprocedure as in Example 9A except the weight ratio of activeprosurfactants Example 5 and Example 6 was adjusted to 85:15respectively.

Example 9C is an example of the preparation of the epoxy dispersion madefrom a 70.30 ratio blend of prosurfactants Example 5 and Example 6respectively. This epoxy dispersion was made by following the sameprocedure as in Example 9A except the weight ratio of activeprosurfactants Example 5 and Example 6 was adjusted to 70:30respectively.

Example 10 is an example of the preparation of the epoxy dispersion madefrom the product of Example 7 prosurfactant according to the invention.

To a resin flask equipped with a heating mantle, an agitator, a nitrogenpurge, a vacuum system and a condenser were added 936.8 grams of EPONResin 828, 285.6 grams bisphenol A and 1.0 gram of triphenylphosphine.The flask was purged with nitrogen and the pressure was reduced to 20.3KPa absolute pressure. The batch was heated with agitation to 130° C.and allowed to exotherm to 194° C. The batch was allowed to cool to 176°C. at atmospheric pressure over 1.5 hours. The batch was then cooled to151° C. and 99.3 grams of propylene glycol monomethyl ether were added.The batch was reflux cooled with reduced pressure to 99° C. Then 84.6grams of Example 7 were added at atmospheric pressure. The batch wasallowed to cool with agitation to 96° C. over 1.8 hours. At this point285.1 grams of deionized water was added to the batch over 2 minutes.The batch was then cooled with reduced pressure to 75° C. at which pointthe epoxy polymer and the epoxy prosurfactant epoxy formed a resin inwater dispersion.

After mixing this dispersion for an additional 1.5 hrs at 37.3 KPaabsolute pressure (to cool the batch to 57° C.) the mean Sa (surfacearea) diameter particle size was 0.869 microns and the mean Dv (volume)diameter particle size was 1.274 microns. At this point the batch wasreturned to atmospheric pressure and 13.0 grams of acetone were added tothe batch. The batch was mixed for 20 minutes at 57° C. and 1.26 gramsof a 50% polypropylene glycol solution of dodecylbenzene sulfonic acidwas added to control the pH to near neutral. The batch was mixed for anadditional 20 minutes and then 26.0 grams of HELOXY Modifier 8 wereadded over 10 minutes. The batch was mixed for 1 hour and then allowedto cool to 22° C. overnight. The next morning the batch was warmed withagitation over 1.25 hours to 53° C.

Then the batch was diluted to 52.2% solids over 2 hours while allowingthe temperature to cool to 32° C. The batch was mixed for an additional20 minutes and then filtered through an 80 mesh filter bag. The particlesize of this final epoxy dispersion was Sa 0.680 and Dv 1.013 microns.The fresh batch viscosity was 1,200 cP at 25° C. The epoxide equivalentweight of the resin content was 513. The pH of the batch after 1 day at49° C. plus 3 day at 25° C. was 7.47 and the viscosity was 1,060 cP at25° C. measured as described in Example 8. As shown in Table IV, thisdispersion had the lowest initial viscosity profile compared to the“state of the art” Example 8 as well as all other examples. Thisdispersion also was the lowest in particle size and had a lower pH withexcellent epoxy equivalent weight stability (see Table III.).

The surfactant of Example 10 is believed to have the followingstructure:

where R is a C9 branched alkyl chain, n is 0, 1, or 2, and x=131 averageobtained by 55 parts X=81+45 parts X=192.

Example 11 is a comparative example of the preparation of the epoxydispersion made from a prosurfactant prepared according to the methoddescribed in Example 5.

To a resin flask equipped with a heating mantle, an agitator, a nitrogenpurge, a vacuum system and a condenser were added 933.7 grams of EPONResin 828 and 288.2 grams bisphenol A. The batch was heated withagitation to 110° C. Then 1.0 gram of triphenylphosphine was added tothe mixture. The batch was heated with agitation to 132° C. and allowedto exotherm as high as 190° C. The batch was then held at 177° C.-190°C. for 45 minutes. The batch was then cooled to 133° C. and 99.3 gramsof propylene glycol monomethyl ether were added. The batch was refluxedand cooled to 105° C. Then 84.0 grams of batch made by Example 5 processbut having a high molecular weight peak content of 30.8%, 2863equivalent weight titrateable nitrogen and 64.8% solids were added atatmospheric pressure. The batch was allowed to cool with agitation to98° C. over 2.25 hours. At this point 285.5 grams of deionized water wasquickly added to the batch over 10 minutes. The batch was then cooledwith reduced pressure to 74° C. at which point the epoxy polymer and theprosurfactant epoxy formed a resin in water dispersion.

After mixing the dispersion for an additional 2.0 hrs at 44.0 KPaabsolute pressure (to cool the batch to 55° C.) the mean Sa (surfacearea) diameter particle size was 0.875 microns and the mean volume (Dv)particle size was 1.324 microns. At this point the batch was returned toatmospheric pressure and 13.0 grams of acetone were added to the batch.The batch was mixed for 20 minutes at 54° C. and 1.3 grams of 50%polypropylene glycol solution of dodecylbenzene sulfonic acid was addedto control the pH. The batch was mixed an additional 20 minutes and then26.0 grams of HELOXY Modifier 8 were added over 10 minutes. The batchwas mixed for 35 minutes at 54° C. and then allowed to cool withoutmixing to 22° C. overnight. The next morning the batch was very slowlyheated up to 53° C. over an hour. The batch was then diluted withdeionized water over 1.5 hours while allowing the temperature to cool to50° C.

The batch was mixed an additional 20 minutes and then filtered throughan 80 mesh filter bag. Samples were further diluted to 55.9%, 53.8%, and52.0% non-volatiles. The batch Brookfield RVDVI viscosities measured thesame day they were diluted were 27,600 cP, 9,560 cP, and 1,700 cPrespectively measured with spindle 5 (or 6 for over 20,000 cP) and 20rpm at 25° C. The initial viscosities (after 1 day at 49° C. plus 2 daysat 25° C. to allow for deairing and pH equilibration) were 22,200 cP,5,980 cP and 920 cP at the respective % solids. The particle size ofthis final epoxy dispersion was Sa 0.835 and Dv 1.301 microns. Theepoxide equivalent weight of the resin content was 518. The pH of thebatch after 1 day at 49° C. plus 1 day at 25° C. was 8.79. Thisdispersion had a low initial viscosity, but both the viscosity and epoxyequivalent weight were not stable and the pH was high. The viscosity ofthis dispersion increased more rapidly during storage at 25° C. comparedto Example 8 as shown in Table IV.

Example 12 is a comparable example of the preparation of the epoxydispersion made from a prosurfactant prepared according to the methoddescribed in Example 6.

To a resin flask equipped with a heating mantle, an agitator, a nitrogenpurge, a vacuum system and a condenser were added 933.5 grams of EPONResin 828 and 288.9 grams bisphenol A. The batch was heated withagitation to 104° C. Then 1.0 gram of triphenylphosphine was added tothe mixture. The batch was heated with agitation to 132° C. and allowedto exotherm as high as 190° C. The batch was then held at 177° C.-190°C. for 55 minutes. The batch was then cooled to 141° C. and 99.3 gramsof propylene glycol monomethyl ether were added. The batch was refluxedand cooled to 109° C. Then 84.7 grams of batch made by Example 6 processbut having a high molecular weight peak content of 27.14%, 2863equivalent weight titrateable nitrogen and 64.2% solids were added atatmospheric pressure. The batch was allowed to cool with agitation to98° C. over 2.0 hours. At this point 285.0 grams of deionized water wasquickly added to the batch over 10 minutes. The batch was then cooledwith reduced pressure to 74° C. at which point the epoxy polymer and theprosurfactant epoxy formed a resin in water dispersion.

After mixing the dispersion for an additional 1.0 hrs at 33.8 KPaabsolute pressure (to cool the batch to 54° C.) the mean Sa diameter(surface area) particle size was 0.836 microns and the mean Dv (volume)particle size was 1.329 microns. At this point the batch was returned toatmospheric pressure and 13.0 grams of acetone were added to the batch.The batch was mixed for 20 minutes at 54° C. and 1.3 grams of 50%polypropylene glycol solution of dodecylbenzene sulfonic acid was addedto control the pH to near neutral. The batch was mixed an additional 20minutes and then 26.0 grams of HELOXY Modifier 8 were added over 10minutes. The batch was mixed for 1 hour. The batch was diluted withdeionized water over 1.5 hours while allowing the temperature to cool to50° C.

The batch was mixed an additional 20 minutes and then filtered throughan 80 mesh filter bag. Samples were further diluted to 55.8%, 53.9%, and52.0% non-volatiles. The batch Brookfield RVDVI viscosities measured thesame day they were diluted were 8,060 cP, 3,660 cP, and 1,680 cPrespectively at measured with spindle 5 and 20 rpm at 25° C. The initialviscosities (after 1 day at 49° C./2 days at 25° C. to allow fordeairing and pH equilibration) were 15,920 cP, 3,360 cP and 1,460 cP atthe respective % solids. The particle size of this final epoxydispersion was Sa 0.873 and Dv 1.288 microns. The epoxide equivalentweight of the resin content was 513. The pH of the batch after 1 day at49° C. plus 1 day at 25° C. was 7.29. Although the pH and epoxyequivalent weight stability of this dispersion was preferred, theparticle size was large and the initial viscosity was higher than thepreferred Example 10 as shown in Tables III and IV).

Example 13 is an example of a co-oxidation of the preferredpolyoxyethylene glycol (PEG) blend of 4000 and 8000 number averagemolecular weights in a ratio of 55 to 45 respectively, to a carboxylicacid functional surfactant.

The preferred polyoxyethylene glycol (PEG) blend of 4000 and 8000 numberaverage molecular weights in a ratio of 55 to 45 (20.0 pounds of PEG4000 diol and 16.36 pounds of PEG 8000 diol) respectively were oxidizedtogether in the same manner as Example 3 (also according to the processoutlined in U.S. Pat. No. 6,956,086 B2 Example 1) as an aqueous solutionto the corresponding dicarboxylic acids. This process was repeated andthe two products were blended. The resulting PEG acids were adjusted to59.4% concentration in water and the average weight per acid of the PEGcarboxylates were measured to be 3629.

Example 14 is an example of the preparation of amido amine prosurfactantcomposition using Example 13 as the starting raw material. The reactorcontents of Example 13 were converted to the amidoamine prosurfactant bythe same process as in Example 5. The resulting prosurfactant had anamine nitrogen equivalent weight of 4065 and a nonvolatile content of63.0%.

Example 15 is an example of the preparation of an epoxy dispersion bythe method described in Example 8 using Example 14 prosurfactant.

The resulting epoxy dispersion from prosurfactant from Example 14 had atypical average micron diameter particle size profile of Dv 0.870, Sa0.623, Dn 0.633 and Dw 0.814. The epoxy equivalent weight of thedispersed polymer was 507, the viscosity was 1,220 cP at 52.2% NV. Thisepoxy dispersion was used with the amine curing agent dispersion inExample 16 to make a high performance primer paint as described inExample 17.

Example 16 is an example of the preparation of an amine curing agentdispersion using prosurfactant from Example 14.

In a similar fashion to the procedure described in U.S. Pat. No.6,277,928 example 1, the prosurfactant of Example 14 was reacted into anexcess solution of EPON 1001X75 in a ratio of 5.5 to 94.5. This epoxyprosurfactant adduct was subsequently reacted into 3 molestriethylenetetramine (TETA) per equivalent of epoxy. After the reactionwas completed the volatiles including 2 moles excess TETA were removedby vacuum distillation. Then one mole of monoepoxy Heloxy 62 was addedper equivalent of unreacted primary amine. This amine functionaladducted polymer was then dispersed in water to give a white dispersionwith an average micron particle size diameter of Dv 0.516 and Sa 0.423.The non-volatile content of this dispersion was 51.6% and thenon-volatile polymer amine value was 257. This amine functional polymerdispersion was used in combination with the Example 15 epoxy dispersionto make the high performance primer paint described in Example 18.

The Momentive SF 1700 paint performance of the example 15 Epoxy andExample 16 Amine Dispersions included a Hours Thru Dry of 1.25 hours, a7 Day Pencil SF1700 of H, and a SF1700 KU Viscosity at Initial and 3hour reviews of 71 and 68 respectively. In contrast, the CommercialStandard Epoxy and Amine Dispersions derived from Example 4prosurfactant included a Hours Thru Dry SF1700 of 1.75 hours, a 7 DayPencil SF1700 of H, and a SF1700 KU Viscosity at Initial and 3 hours of54 and 78 respectively.

Example 17 is an example of the preparation of an amine curing agentdispersion using prosurfactant from Example 7.

In a similar fashion to the procedure described in U.S. Pat. No.6,277,928 example 1, the prosurfactant of Example 7 was reacted into anexcess solution of EPON 1001×75 in a ratio of 5.5 to 94.5. This epoxyprosurfactant adduct was subsequently reacted into 3 molestriethylenetetramine (TETA) per equivalent of epoxy. After the reactionwas completed the volatiles including 2 moles excess TETA were removedby vacuum distillation. Then one mole of monoepoxy Heloxy 62 was addedper equivalent of primary amine. This amine functional adducted polymerwas then dispersed in water to give a white dispersion with an averagemicron particle size diameter of Dv 0.331 and Sa 0.219. The non volatilecontent of this dispersion was 51.2% and the non volatile amine polymeramine value was 242. This amine functional polymer dispersion was usedin combination with Example 15 epoxy dispersion to make the highperformance primer coated described in Example 18.

The Momentive SF 1700 paint performance of the example 15 Epoxy andExample 17 Amine Dispersions included a Hours Thru Dry of 1.5 hours, a 7Day Pencil SF1700 of F+, and a SF1700 KU Viscosity at Initial and 3 hourreviews of 68 and 73 respectively. In contrast, the Commercial StandardEpoxy and Amine Dispersions derived from Example 4 prosurfactantincluded a Hours Thru Dry SF1700 of 1.75 hours, a 7 Day Pencil SF1700 ofF+, and a SF1700 KU Viscosity at Initial and 3 hour of 54 and 78respectively.

Example 18 is an example of the preparation of Primer paints fromdispersions made with above amidoamine prosurfactants as defined byMomentive published Starting Point Formulation 1700 as follows.

300.0 lbs (33.33 gallons) of the epoxy resin dispersion described hereinin Example 15 was mixed with 26.0 lbs (2.95 gallons) of the PPHpropylene glycol phenyl ether (from Dow Chemical), 3.0 lbs (0.35gallons) of the EFKA® 2526 Defoamer (from CIBA Specialty Company) 100.0lbs (3.1 gallons) of the Ti-Pure® R-960 pigment (from Du Pont), 100.0lbs (4.12 gallons) of the 10 ES WOLLASTOCOAT® (from NYCO Minerals, Inc.)67.0 lbs (1.83 gallons) of the Sparmite™ A barytes (from ElementisPigments Inc.), 94.7 lbs (3.98 gallons) of the HALOX® SW-111 (from HALOXPigments), 7.0 lbs (0.3 gallons) of the wet ground mica, 325 Mesh (fromFranklin Industrial Minerals). The mixture was subjected to a high speeddisperse process to provide a texture of 5-6 Hegman Scale. The mixingspeed was reduced and 107.5 lbs (11.94 gallons) of the EPI-REZ Resin6520-WH-53 (from Momentive Specialty Chemicals), 8.6 lbs (0.98 gallons)of the CoatOSil™ 1770 Silane (from Momentive Performance Products), and142.9 (7.12 gallons) of water was then added. The mixture at this pointcomprises 959.7 lbs (80.0 gallons) of composition. To this mixture wasadded 180 lbs (19.78 gallons) of the curing agent dispersion of Example17 as described herein (from Momentive Specialty Chemicals) and 2 lbs(0.22 gallons) of the Raybo 60 flash rust inhibitor (from Raybo). Thecomposition was formulated at 1:1 stoichiometry (epoxy:amineequivalents).

Example 19 is an example of the preparation of epoxy dispersion forfiber sizing using prosurfactant Example 7.

The prosurfactant from Example 7 may also be used to make waterborneepoxy dispersions for fiber sizing or adhesives that contain reduced orno organic volatile solvents. To a 3 liter resin pot was added 99.7grams liquid epoxy resin, EPON 828, 102.5 grams of aqueous Example 7prosurfactant and 200.0 grams of deionized water. An agitator and achilled water condenser were added to the flask to contain the watervapor during heating the batch with mixing to 180° F.

The batch was allowed to react for 1 hour at this temperature and then1.6 grams of dodecylbenzene sulfonic acid was added. The batch was thendiluted further with 200.0 grams water, allowed to cool to 160° F. andthen 1,141.8 grams of additional EPON 828 was added over 30 minutes withgood mixing. The batch was allowed to cool to 125° F. with mixing over 2hours, and then 140.0 grams of water was added followed by 0.7 gramsRhodaline 640 defoamer. The batch was mixed for 1.5 hours at 125-132° F.and then diluted to 54.2% NV with an additional 340.3 grams of waterwith 11.0 grams of OptifloH600VF added. After allowing the batch to coolslowly to 25° C., without mixing for 16 hours, the viscosity was 1,240cP measured by Brookfield spindle 5 at 20 rpm. The particle size was Dv0.71, the epoxy equivalent weight of the dispersed polymer was 197.2 andthe pH was 6.9.

Example 20 is the preparation of an amidoamine prosurfactant compositionusing Example 13 and isodecyloxypropyl-1,3-diaminopropane as thestarting raw material.

To a 3-liter, 4-neck resin flask equipped with agitation, a heatingmantle, a nitrogen sparge and a vacuum system were added 2195.1 grams ofaqueous, carboxylated polyoxyethylene oxide from Example 13. The waterwas removed from the product of Example 13 by vacuum distillation at 91°C. Then 118.2 grams isodecyloxypropyl-1,3-diaminopropane were added tothe flask. The flask was purged with nitrogen and heated to 215° C. atthe maximum heating rate set by the temperature controller. Waterdistilled from the reaction mixtures as the amide formation reactionproceeded. The reaction mixtures were held for 3 hours at 165° C. undernitrogen with a xylene azeotrope and trap to collect water ofamidification. The xylene and residual water were removed under reducedpressure with a strong nitrogen sparge. The amidoamine product was thencooled to approximately 90° C. and diluted with water 65.0% solids. Theamine nitrogen equivalent weight of the aqueous capped amidoaminepolymer (solids basis) was determined to be 3610. This prosurfactant wasused to make epoxy dispersion Example 21 which was low viscosity.

Example 21 is an example of the preparation of an Epoxy dispersion bythe method described in Example 10 using Example 20 prosurfactant.

The dispersion was made by the same procedure as Example 10 but usingprosurfactant Example 20. The resulting epoxy dispersion using theExample 20 prosurfactant had a typical average micron diameter particlesize profile of Dv 1.39, Dn 0.84 and Dw 1.14. The epoxy equivalentweight of the dispersed polymer was 529, the viscosity was 360 cps at53.75% NV and the dispersion pH was 8.38 after 24 hours at 25° C.

TABLE III Disper- sion # 1 2 3 4 5 6 Prosur- 4 5 6 5/6 7 14 factantExam- ple Epoxy 8 11 12 9 A 10 15 Disper- sion Exam- ple Sur- 4600 40008000 4000/8000 4000/8000 4000/ factant 55/45 Blend 55/45 co- 8000 PEGamido- 55/45 co- aminified oxidized % sur- 3.40 3.40 3.40 3.40 3.40 3.40factant Initial 2,600 1700 1680 2020 1200 1,220 Vis- cosity Particle0.942/ 1.301/ 1.288/ 1.248/ 1.013/ 0.87/ Dv size 0.743 0.835 0.873 0.8620.680 0.623 μm/SA, pH 8.60 8.79 7.29 8.18 7.47 6.74 (Initial) pH 9.239.15 9.04 9.04 9.03 9.26 final* Shelf >15 9 >15 >15 >15 >10 life months*The pH final was the measurement of the pH at time at room temperatureto double (or exceed 6,000 cP) viscosity.

Table IV below provides for a comparison of viscosity stability withlonger shelf life at 25° C. As shown below, the epoxy dispersion madefrom the blends (Examples 9 and 10) provided equivalent or improvedviscosity results as compared to the prior art epoxy dispersions(Examples 8, 11, and 12). The following viscosity measurements are incentipoise (cP or cps).

TABLE IV Ex. #9A: 55/45 Ex. #10: 55/45 Co- Ex. #11: Ex. #8: Ex. #12:Blend of Amid. Blend of Months 4000 MW 4600 MW 8000 MW 4000 Mw/8000 Mw4000 Mw/8000 Mw  0 1,700 2,600 1,680 2,020 1,200  8 4,720 4,200 2,4003,340 1,620 10 6,840 4,220 2,440 4,140 1,760 15 19,620 4,360 2,820 4,2801,820 % − Δ 46 48 13 27 26 % + Δ 1,054 68 68 112 52 Δ Sum* 1,100 116 81139 78 μm Particle 0.835/1.301 0.743/0.942 0.873/1.288 0.862/1.4280.680/1.013 size Sa/Dv *Brookfield Viscosity spindle 5 at 20 rpm at 25°C.

Table V below provides for a comparison of epoxy equivalent weightstability at 25° C. over 15 months between compositions as describedherein and prior art compositions as detailed. Invention most preferredexample 10 and preferred example 9 have significantly improved epoxyequivalent weight stability over state of the art control Examples 8 and11.

TABLE V Months at Control Blend Co-amid PEG 4000 PEG 8000 25° C. Ex. 8Ex. 9A Ex. 10 Ex. 11 Ex. 12  0 504 516 513 518 513 15 581 575 560 592562 % Δ 15 11 9 14 10

Table VI below and the graph as shown in FIG. 1, provide for acomparison of particle size stability between compositions as describedherein and prior art composition as detailed. Table VI illustrates theparticle size stability of examples 9 and 10 as described herein overthe state of the art control as shown in Example 8. FIG. 1, illustratesa graph comparing epoxy dispersion particle size stability at 25° C. forepoxy dispersions as formed herein in Examples 9A, 9B, and 9Cas comparedto the prior art Examples 11 and 12.

TABLE VI control Ex blend Ex Co-amide Ex Dv Change 8 9 10 Δ 0.613 0.4200.312 Initial Dv 0.942 1.248 1.073 Dv @ 10 months 1.555 1.668 1.385

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein.

What is claimed is:
 1. An amidoamine composition, comprising a reactantproduct of: an acid terminated polyoxyalkylene composition of two ormore acid terminated polyoxyalkylene polyol compounds, wherein the acidterminated polyoxyalkylene composition having a polydispersity of 1.1 orgreater and the two or more acid terminated polyoxyalkylene polyolcompounds have from about 50% to about 100% of carboxylic end groupsoxidized from hydroxyl end groups; and a diamine compound comprising afirst amine substituent group of a primary amine substituent group and asecond amine substituent group of a primary amine substituent group or asecondary amine substituent group, wherein the reaction productcomprises an amidoamine compound having the formula of:

wherein each of R₁ and R₂ comprises a hydrogen atom or a substituentgroup selected from the group consisting of a branched or linearaliphatic, a cycloaliphatic, an aromatic substituent group andcombinations thereof, having 1 to 21 carbon atoms, with at least one ofR₁ and R₂ comprising a hydrogen atom, R₃ is a divalent hydrocarbonsubstituent group selected from the group consisting of a branched orlinear aliphatic, a cycloaliphatic, an aromatic substituent group, andcombinations thereof, having 2 to 18 carbon atoms, n is an averagenumber from about 18 to about 500, X is a hydrogen atom or a substituentgroup selected from the group consisting of a methyl substituent, anethyl substituent, a hydroxymethyl substituent group, and combinationsthereof, and Y is a hydrogen atom or a substituent group selected fromthe group consisting of a methyl substituent, an ethyl substituent, ahydroxymethyl substituent group, and combinations thereof.
 2. Thecomposition of claim 1, wherein the amidoamine compound comprises anamine value from about 8 to about
 30. 3. The composition of claim 1,wherein the diamine compound comprises two primary amine substituentgroups with the diamine having the formula:H₂N—R₃—NH₂, wherein R₃ is a divalent hydrocarbon substituent groupselected from the group consisting of a branched or linear aliphatic, acycloaliphatic, an aromatic substituent group, and combinations thereof,having 2 to 18 carbon atoms.
 4. The composition of claim 3, wherein thediamine compound is provided at a stoichiometric excess of aminesubstituent groups to carboxylic end groups of the acid terminatedpolyoxyalkylene composition.
 5. The composition of claim 3, wherein thereactant product further comprises a monoepoxy compound.
 6. Thecomposition of claim 1, wherein the diamine compound comprises a primaryamine substituent group and a secondary amine substituent group with thediamine having the formula:R₁—HN—R₃—NH₂, wherein R₁ is a branched or linear aliphatic, acycloaliphatic, or an aromatic divalent substituent group having 1 to 21carbon atoms and R₃ is a divalent hydrocarbon substituent group selectedfrom the group consisting of a branched or linear aliphatic, acycloaliphatic, an aromatic substituent group, and combinations thereof,having 2 to 18 carbon atoms.
 7. The composition of claim 6, wherein theR₁ substituent group further comprises an end group selected from thegroup consisting of a methyl group, a hydroxyl group, and combinationsthereof, and the R₃ substituent group further comprises an end groupselected from the group consisting of a methyl group, a hydroxyl group,and combinations thereof.
 8. The composition of claim 7, wherein the R₁substituent group, the R₃ substituent group, or both, further comprisesone or more non-reactive oxygen or nitrogen atoms in the backbone of thesubstituent group.
 9. The composition of claim 1, wherein each of thetwo or more polyoxyalkylene polyol compounds are reacted with thediamine compound separately and then combined to form the amidoaminecomposition.
 10. A method for forming an amidoamine composition,comprising: providing an acid terminated polyoxyalkylene composition oftwo or more acid terminated polyoxyalkylene polyol compounds, whereinthe acid terminated polyoxyalkylene composition having a polydispersityof 1.1 or greater and the two or more acid terminated polyoxyalkylenepolyol compounds have from about 50% to about 100% of carboxylic endgroups oxidized from hydroxyl end groups; providing a diamine compoundcomprising a first amine substituent group of a primary aminesubstituent group and a second amine substituent group of a primaryamine substituent group or a secondary amine substituent group; andreacting the acid terminated polyoxyalkylene composition and the firstdiamine compound to form a reactant product, wherein the reactionproduct comprises an amidoamine compound having the formula of:

wherein each of R₁ and R₂ comprises a hydrogen atom or a substituentgroup selected from the group consisting of a branched or linearaliphatic, a cycloaliphatic, an aromatic substituent group andcombinations thereof, having 1 to 21 carbon atoms, with at least one ofR₁ and R₂ comprising a hydrogen atom, R₃ is a divalent hydrocarbonsubstituent group selected from the group consisting of a branched orlinear aliphatic, a cycloaliphatic, an aromatic substituent group, andcombinations thereof, having 2 to 18 carbon atoms, n is an averagenumber from about 18 to about 500, X is a hydrogen atom or a substituentgroup selected from the group consisting of a methyl substituent, anethyl substituent, a hydroxymethyl substituent group, and combinationsthereof, and Y is a hydrogen atom or a substituent group selected fromthe group consisting of a methyl substituent, an ethyl substituent, ahydroxymethyl substituent group, and combinations thereof.
 11. Themethod of claim 10, wherein the amidoamine compound comprises an aminevalue from about 8 to about
 30. 12. The method of claim 10, wherein theproviding the diamine compound comprises providing a diamine compoundhaving two primary amine substituent groups with the formula:H₂N—R₃—NH₂, wherein R₃ is a divalent hydrocarbon substituent groupselected from the group consisting of a branched or linear aliphatic, acycloaliphatic, an aromatic substituent group, and combinations thereof,having 2 to 18 carbon atoms.
 13. The method of claim 12, wherein theproviding the diamine compound comprises providing the diamine compoundat a stoichiometric excess of amine substituent groups to carboxylic endgroups of the acid terminated polyoxyalkylene composition.
 14. Themethod of claim 12, further comprising reacting the reaction productwith a monoepoxy-containing composition.
 15. The method of claim 10,wherein the providing the diamine compound comprises providing a diaminecompound having a primary amine substituent group and a secondary aminesubstituent group with the diamine having the formula:R₁—HN—R₃—NH₂, wherein R₁ is a branched or linear aliphatic, acycloaliphatic, or an aromatic substituent group having 1 to 21 carbonatoms and R₃ is a divalent hydrocarbon substituent group selected fromthe group consisting of a branched or linear aliphatic, acycloaliphatic, an aromatic substituent group, and combinations thereof,having 2 to 18 carbon atoms.
 16. The method of claim 15, wherein the R₁substituent group further comprises an end group selected from the groupconsisting of a methyl group, a hydroxyl group, and combinationsthereof, and the R₃ substituent group further comprises an end groupselected from the group consisting of a methyl group, a hydroxyl group,and combinations thereof.
 17. The method of claim 16, wherein the R₁substituent group, the R₃ substituent group, or both, further comprisesone or more non-reactive oxygen or nitrogen atoms in the backbone of thesubstituent group.
 18. The method of claim 10, wherein each of the twoor more polyoxyalkylene polyol compounds are reacted with the diaminecompound separately to form a first and second amidoamine compound, andfurther comprising intermixing the first and second amidoaminecompounds.
 19. The method of claim 10, further comprising reacting thereactant product with an epoxy composition to form an epoxy functionalamidoamine composition.
 20. The method of claim 19, wherein the epoxycomposition comprises a di-epoxy component.
 21. The method of claim 20,wherein the di-epoxy component comprises a di-epoxy resin or a mixtureof a di-epoxy resin and a phenolic compound.
 22. The method of claim 19,wherein the epoxy composition comprises at least one epoxy resin havinga functionality of greater than 0.8 epoxide groups per molecule.
 23. Themethod of claim 19, wherein the epoxy composition comprises astoichiometric excess of epoxy substituent groups to amine groups andwater, and the epoxy functional amidoamine composition comprises anaqueous epoxy resin dispersion.
 24. The method of claim 23, wherein theepoxy-functional surfactant comprises from about 1 wt. % to about 20 wt.% of the dispersion.
 25. The method of claim 19, wherein the epoxyfunctional amidoamine composition comprises an epoxy-functionalsurfactant having the formula:

wherein m is from 1 to 11, n is from 1 to 3, q is from 0 to 8, each p isfrom about 18 to about 500, X is a hydrogen atom, a methyl substituent,an ethyl substituent, a hydroxymethyl substituent group, subsetsthereof, or combinations thereof, each Y is a hydrogen atom, a methylsubstituent, an ethyl substituent, a hydroxymethyl substituent group, orcombinations thereof, and R₁₇ is an alkyl group, an aryl group, an acylgroup, or combinations thereof.
 26. The method of claim 19, furthercomprising reacting the epoxy functional amidoamine composition with apolyamine compound.